CN102387856B - The catalyst for diesel applications partition - Google Patents

The catalyst for diesel applications partition Download PDF

Info

Publication number
CN102387856B
CN102387856B CN201080014918.1A CN201080014918A CN102387856B CN 102387856 B CN102387856 B CN 102387856B CN 201080014918 A CN201080014918 A CN 201080014918A CN 102387856 B CN102387856 B CN 102387856B
Authority
CN
China
Prior art keywords
washcoat
diesel
catalyst
oxidation catalyst
palladium
Prior art date
Application number
CN201080014918.1A
Other languages
Chinese (zh)
Other versions
CN102387856A (en
Inventor
J·B·霍克
J·C·德特兰
Original Assignee
巴斯夫公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US16757509P priority Critical
Priority to US61/167,575 priority
Priority to US12/755,032 priority
Priority to US12/755,032 priority patent/US8637426B2/en
Application filed by 巴斯夫公司 filed Critical 巴斯夫公司
Priority to PCT/US2010/030226 priority patent/WO2010118125A2/en
Publication of CN102387856A publication Critical patent/CN102387856A/en
Application granted granted Critical
Publication of CN102387856B publication Critical patent/CN102387856B/en

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/0006Catalysts containing parts with different compositions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56Platinum group metals
    • B01J23/63Platinum group metals with rare earths or actinides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/12Noble metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44Noble metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74Noble metals
    • B01J29/7415Zeolite Beta
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/024Multiple impregnation or coating
    • B01J37/0246Coatings comprising a zeolite
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/103Oxidation catalysts for HC and CO only
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/10Noble metals or compounds thereof
    • B01D2255/102Platinum group metals
    • B01D2255/1021Platinum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/10Noble metals or compounds thereof
    • B01D2255/102Platinum group metals
    • B01D2255/1023Palladium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/90Physical characteristics of catalysts
    • B01D2255/902Multilayered catalyst
    • B01D2255/9022Two layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/01Engine exhaust gases
    • B01D2258/012Diesel engines and lean burn gasoline engines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9459Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
    • B01D53/9477Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00Surface coverings
    • F01N2510/06Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • F01N2510/0682Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having a discontinuous, uneven or partially overlapping coating of catalytic material, e.g. higher amount of material upstream than downstream or vice versa
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00Surface coverings
    • F01N2510/06Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • F01N2510/0684Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having more than one coating layer, e.g. multi-layered coatings
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066Selective catalytic reduction [SCR]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/10Internal combustion engine [ICE] based vehicles
    • Y02T10/20Exhaust after-treatment
    • Y02T10/22Three way catalyst technology, i.e. oxidation or reduction at stoichiometric equivalence ratio

Abstract

公开了用于处理先进燃烧发动机废气排放物例如使柴油发动机和先进燃烧柴油发动机排放的未燃烃(HC)和一氧化碳(CO)氧化以及使氮氧化物(NOx)还原的氧化催化剂复合物、方法和系统。 Discloses a process for advanced combustion engine exhaust emissions such as the diesel engine and unburned hydrocarbons (HC) and oxide monoxide (CO) emissions from diesel engines advanced combustion and nitrogen oxides (NOx) reduction of the composite oxide catalyst, a method and systems. 更具体地,公开了包含至少两个洗涂层的洗涂层复合物,其中第一洗涂层包含钯组分,第二洗涂层含有铂,并且铂总量的至少大约50%位于催化剂后部。 More particularly, the disclosed washcoat comprising at least two washcoat composite, wherein the first washcoat layer comprising a palladium component, a second washcoat comprising platinum, and at least about 50% of the platinum catalyst is located rear.

Description

用于柴油应用的分区催化剂 The catalyst for diesel applications partition

[0001] 相关申请的交叉引用 CROSS [0001] REFERENCE TO RELATED APPLICATIONS

[0002] 根据35USC§119(e),本发明要求享有第61/167,575号美国临时申请的优先仅,其通过引用并入本文。 [0002] Only, which is incorporated herein by reference in accordance with 35USC§119 (e), the present invention claims the benefit of No. 61 / 167,575 U.S. Provisional Application priority.

技术领域 FIELD

[0003] 本发明的实施方案涉及分区设计的氧化催化剂。 [0003] The embodiments of the present invention relates to an oxidation catalyst designed partition. 更具体地,实施方案涉及包含耐火金属氧化物负载体(例如含Ce负载体)中的Pt和Pd的分区催化剂配方,及其减少柴油发动机和高级燃烧柴油发动机系统中的一氧化碳和烃的用途。 More particularly, embodiments relate to a partition comprising refractory metal oxide supported catalyst formulations (e.g. load-containing body Ce) of Pt and Pd, and reduce the use of advanced diesel engines and diesel engine combustion system of carbon monoxide and hydrocarbons.

背景技术 Background technique

[0004] 稀薄燃烧发动机(例如柴油发动机和稀薄燃烧汽油发动机)的运行为用户节约了燃料,并且由于其在燃料稀薄的条件下以高空气/燃料比率运行,与火花点火化学计量比汽油发动机(spark-ignited stoichiometric gasoline engine)相比,其排放的气态经和一氧化碳显著较少。 Run [0004] The lean-burn engines (e.g. diesel engines and lean-burn gasoline engines) for the user to save fuel, and because of its operation at high air / fuel ratio under fuel-lean conditions, the spark ignition stoichiometric gasoline engine ( spark-ignited stoichiometric gasoline engine) compared to significantly less carbon monoxide and gaseous by their emissions. 柴油发动机的排放物包括颗粒物质(PM)、氮氧化物(NOx)、未燃烃(HC)和一氧化碳(CO) 13NOx是用于描述多种化学类型的氮氧化物的术语,其中包括一氧化氮(NO)和二氧化氮(N〇2)。 Emissions from diesel engines include particulate matter (the PM), nitrogen oxides (NOx), unburned hydrocarbons (HC) and carbon monoxide (CO) 13NOx term nitrogen oxides for various chemical of the type described, which comprises an oxide nitrogen (NO) and nitrogen dioxide (N〇2).

[0005] 用于处理柴油发动机废气和汽油发动机废气的催化剂系统之间存在很多差异。 There are many differences between the catalyst system [0005] for the treatment of diesel engine exhaust and gasoline engine exhaust gas. 这两种发动机类型和其运行之间的一个显著差异是汽油发动机是火花点火式并且在理论空燃比中运行,柴油发动机是压缩点火式发动机,其在空气大大过量的条件下运行。 A significant difference between the type of engine and its operation is both a gasoline engine and a spark ignition operation in the theoretical air-fuel diesel engine is a compression-ignition engine, which is operated at conditions of a large excess of air. 这两种类型的发动机的排放物非常不同并且需要完全不同的催化剂方案。 Both types of emissions of the engine are very different and require a different catalyst solution. 由于柴油发动机中形成大量的NO x和颗粒排放物,通常柴油发动机排放物的处理比汽油发动机排放物的处理更为复杂。 Because a large number of NO x and particulate emissions from diesel engines is formed, the process is usually a diesel engine emissions process more complex than a gasoline engine emissions.

[0006] 废气颗粒物质的两个主要组分是可溶性有机成分(SOF)和烟灰成分(烟灰过滤器)JOF在烟灰上凝结成层,其来源于未燃烧的柴油燃料和润滑油。 [0006] The two main components of the exhaust gas particulate matter is soluble organic fraction (SOF) and soot fraction (soot filter) JOF condenses on the soot in layers, which is derived from the diesel fuel and lubricating oil unburned. 根据废气的温度,SOF在柴油废气中可以以气态或者液态(液体冷凝物的小液滴)存在。 The temperature of the exhaust gas, SOF can exist in a gaseous or liquid (droplets of liquid condensate) in the diesel exhaust. 烟灰主要由碳颗粒组成。 Composed mainly of carbon soot particles. 由于颗粒微小,柴油废气的颗粒物质极易吸入,这在较高暴露水平下造成健康危胁。 Because tiny particles, diesel exhaust particulate matter easily inhaled, which pose a health threat at higher exposure levels. 此外,SOF 含有多环芳香烃,其中一些是疑似致癌物。 Further, the SOF containing polycyclic aromatic hydrocarbons, some of which are suspected carcinogens.

[0007] 利用新的先进燃烧技术(例如均质充量压燃(Homogeneous Charge Compression Ignition(HCCI))的柴油发动机通过点火前使发动机气缸内部燃烧火焰的温度降低和增加燃料供给的一致性和混合度,将能够减少排放到发动机外的NO x和颗粒物质(PM)。与传统柴油发动机排放的废气相比,通常进行任何处理前所排放的废气含有显著减少的颗粒物质和N0 X。在一些情况下,这种先进燃烧柴油发动机排放的NOx比传统柴油发动机排放的NOx少2至3倍。但是,在将燃烧过程转变为较低的NO x和PM排放的过程中,CO和经(HC)排放的总量将增加,所形成的HC的性质将发生变化(例如可能产生更多的甲烷),并且废气温度较低。在一些情况下,先进燃烧柴油发动机的CO和HC排放量比传统柴油发动机的CO和HC排放量高50 %至大约100%。由于这些废气特性对现有柴油排放催化制品技术提出了重大挑战, [0007] The use of new, advanced combustion technologies (e.g., homogeneous charge compression ignition (Homogeneous Charge Compression Ignition (HCCI)) by a diesel engine before ignition internal combustion engine cylinder to reduce temperature of the flame and increasing the fuel supply and mixing consistency degree, will be able to reduce emissions of nO x and particulate matter to the outside of the engine (PM). compared with the conventional diesel engine exhaust emissions, exhaust gas treatment is usually carried out before any significant reduction in emissions containing particulate matter and in some N0 X. case, this advanced combustion NOx emissions from a diesel engine 2 to 3 times less than conventional diesel engine NOx emissions. However, when the combustion process into low emissions of NO x and PM's, CO and by (HC ) emissions will increase, the nature of HC will be formed (e.g., may produce more methane) changes, and the exhaust gas temperature is low. in some cases, advanced combustion diesel engine CO and HC emissions compared to conventional CO and HC emissions from a diesel engine by 50% to about 100% due to the exhaust gas characteristics of these prior art diesel exhaust catalyst article presents a significant challenge, 要新的催化剂配方,以符合日益严格的规章制度,例如Euro 6和US Tier 2Bin 5。 To the new catalyst formulations to meet increasingly stringent regulations, such as Euro 6 and US Tier 2Bin 5.

[0008] 已知利用包含事先涂于耐火金属氧化物负载体上的贵金属的氧化催化剂来处理柴油发动机的废气,以通过将烃和一氧化碳气体污染物氧化成为二氧化碳和水而使这些污染物转化。 [0008] The previously known to utilize an exhaust gas comprising a noble metal oxidation catalyst coated on the refractory metal oxide support treated diesel engine, hydrocarbon and carbon monoxide gaseous pollutants by oxidation to carbon dioxide and water, the conversion of these contaminants. 这种催化剂通常包含于被称为柴油氧化催化剂(DOC)或者更简单地被称为催化转化剂或催化剂中,所述催化剂置于柴油动力系统的废气流通道中,以在废气排向大气前将其处理。 Such catalysts are referred to generally comprise a diesel oxidation catalyst (DOC) or more simply referred to as a catalytic converter or a catalyst, the catalyst is placed in a diesel powered system in an exhaust gas flow path, the exhaust emission to the atmosphere prior to the its processing. 通常柴油氧化催化剂形成于陶瓷或者金属基材的载体上(例如如本文中下面所描述的流通式单片载体),所述载体上沉积一种或者多种催化剂洗涂层复合物。 Typically in a diesel oxidation catalyst is formed (e.g., flow-through monolithic carrier as described herein below) on a ceramic or metal support substrate, depositing on said support one or more composite catalyst washcoat. 除了使气态HC和CO排放物以及颗粒物质(S0F成分)转化之外,含有铂族金属(通常涂于耐火氧化物负载体上)的氧化催化剂促进一氧化氮(NO)氧化为NO 2。 In addition to gaseous HC and CO emissions and particulate matter (S0F are component) other than the conversion, an oxidation catalyst containing a platinum group metal (typically coated on a refractory oxide support) promote nitric oxide (NO) is oxidized to NO 2.

[0009] 用于处理内燃发动机废气的催化剂在相对低温的运行期间例如发动机运行的初始冷启动期效率较低,因为发动机废气的温度不足够高,不能有效地催化废气中有毒组分的转化。 The internal combustion engine exhaust treatment catalyst [0009] The low initial cold start, for example, the efficiency of engine operation during a relatively low temperature operation, since the temperature of the engine exhaust gas is not high enough, can not effectively catalyze the conversion of toxic components in the exhaust gas. 已知含有涂于耐火氧化物负载体上的铂族金属的氧化催化剂可以用于处理柴油发动机排放的废气。 Known platinum group metal-containing oxidation catalyst coated on the exhaust gas on the refractory oxide support may be used for treatment of diesel engine emissions. 铂(Pt)是DOC中在稀薄条件下和在燃料硫存在下高温老化后使CO和HC氧化的有效金属。 Platinum (Pt) is the DOC under lean fuel conditions and in the presence of CO and HC sulfur oxide after high-temperature aging active metal. 另一方面,对于CO和HC的氧化,富含Pd的DOC催化剂通常显示较高的点燃温度,特别是当用于处理含有高水平硫的废气(来源于高硫含量的燃料)或者与HC储存材料一起使用时。 On the other hand, for the oxidation of CO and HC, the DOC enriched Pd catalysts typically exhibit high ignition temperature, in particular when the exhaust gas (from a high sulfur content fuel) for processing and contains high levels of sulfur or a HC storage materials used together. 特定组分的"点燃"温度是所述组分的50%发生反应的温度。 Specific component "ignition" temperature is the temperature of 50% of the components react. 含有Pd的DOC可以抑制Pt使烃转化和/或使NO x氧化的活性,并且还可以使催化剂对硫中毒更加易感。 DOC Pt Pd-containing hydrocarbon conversion can be suppressed and / or oxidation of the active NO x, the catalyst and may also be more susceptible to sulfur poisoning. 这些特性通常阻碍了富含Pd的氧化催化剂在稀薄燃烧运行中的使用,特别是对于大部分行驶条件下发动机温度保持在250°C以下的轻型柴油应用。 These characteristics usually prevents the use of enriched Pd oxidation catalyst in the lean combustion operation, particularly light-duty diesel applications for most driving conditions of the engine is maintained at a temperature of 250 ° C or less.

[0010] 尽管铂(Pt)对于CO和HC具有优良的点燃特性并且因而在历史上是用于去除柴油发动机废气的催化剂复合物中贵金属的优先选择,最近钯(Pd)由于其相对较低的成本而引起更大兴趣。 [0010] Although platinum (Pt) for CO and HC having excellent ignition properties and therefore is used in preference history removing the diesel engine exhaust catalyst composite noble metal, recently palladium (Pd) due to its relatively low costs caused by greater interest. 在一些情况下,已经证明钯适合与铂同时用于DOC催化剂中以减少铂的所需量,尽管其对硫更加敏感并且活性稍弱(基于重量)。 In some cases, it has been demonstrated for both platinum and palladium for DOC catalyst to reduce the amount of platinum required, although it is more sensitive to sulfur and weaker activity (by weight). 事实上,Pt和Pd的组合比单独的Pt更具活性。 In fact, a combination of Pt and Pd is more active than Pt alone. 由于钯在DOC催化剂中的活性较低,确保其以不抑制其性能的方式位于DOC催化剂中是十分重要的。 Due to the low activity of the palladium in the DOC catalyst, which is to ensure that the performance does not inhibit the DOC catalyst positioned manner is important.

[0011] 储氧组分(例如铈)通常不与DOC混合,因为其结合导致铂保持氧化状态。 [0011] The oxygen storage component (e.g., Ce) is generally not mixed with the DOC, since it results in conjunction with the oxidation state of the platinum remains. 由于正常的柴油发动机在持续稀薄条件下运行,铂没有机会被还原成活性金属形式。 Due to normal diesel engine operation under continuous lean conditions and platinum no chance of being reduced to the active metal form.

[0012] 随着排放的规章制度日益严格,开发提供改良性能(例如较低的点燃温度)的柴油氧化催化系统是持续目标。 [0012] With increasingly stringent emissions regulations developed to provide improved performance (e.g. lower ignition temperature) of the diesel oxidation catalyst system is a continuing goal. 尽可能有效地利用DOC组分(例如钯)也是一个目标。 DOC using components (such as palladium) is also a goal as effectively as possible.

[0013] 发明概述 [0013] Summary of the Invention

[0014] 本发明的一个方面是针对用于去除发动机废气排放物的氧化催化剂复合物,包括具有一定长度、入口端和出口端的载体基材,以及载体上的柴油氧化催化剂催化材料,包括第一洗涂层区和第二洗涂层区的柴油氧化催化剂催化材料。 [0014] An aspect of the present invention is directed to an oxidation catalyst composite for removing the engine exhaust emissions, including having a length, the inlet and outlet ends of the carrier substrate, a diesel oxidation catalyst and a catalytic material on a carrier, comprising a first diesel oxidation zone and a second washcoat zone containing catalyst washcoat catalytic material. 第一洗涂层区包含第一洗涂层和第一耐火金属氧化物负载体,所述第一洗涂层含有铂(Pt)和钯(Pd)组分中的一种或者多种。 The first washcoat layer comprising a first washcoat zone and the first refractory metal oxide support, the first washcoat layer comprises platinum (Pt) and palladium (Pd) or more of one of the components. 第一洗涂层区与载体基材的入口端相邻。 The inlet end of the first washcoat zone adjacent the carrier substrate. 第二洗涂层区包含第二洗涂层和第二耐火金属氧化物负载体,所述第二洗涂层含有铂和钯组分中的一种或者多种。 The second washcoat layer comprising a second washcoat zone and a second refractory metal oxide support, the second washcoat layer comprises platinum and palladium or more components. 第二洗涂层区与载体基材的出口端相邻。 The second washcoat layer region adjacent to the outlet end of the carrier substrate. 钯组分总量的至少50%位于第一洗涂层区,并且铂组分总量的至少50 %位于第二洗涂层区。 At least 50% of the palladium component located in the first washcoat zone, and at least 50% of the total amount of the platinum component in the second washcoat zone.

[0015] 在一个实施方案中,第二洗涂层区基本不含钯。 [0015] In one embodiment, the second washcoat zone is substantially free of palladium. 在一个或者多个实施方案中,第一洗涂层区延伸至基材的全长,并且第二洗涂层区与第一洗涂层区的至少一部分重叠。 In one or more embodiments, the first washcoat zone extends to the full length of the substrate, and the second washcoat zone overlaps with at least a portion of the first washcoat zone. 在一个或者多个实施方案中,第一洗涂层区从入口端延伸至基材长度的大约5%至95%,第二洗涂层区从出口端延伸至基材长度的大约5%至95%。 In one or more embodiments, the first washcoat zone extending from the inlet end to the length of the substrate is about 5% to 95%, the second washcoat zone extends from the outlet end to a length of the substrate to about 5% 95%.

[0016] 在一个或者多个实施方案中,第一洗涂层区和第二洗涂层区相互重叠。 [0016] In one or more embodiments, the first washcoat zone and the second washcoat layer overlap region. 根据一个或者多个实施方案,铂和钯以铂总量与钯总量的比率从大约1:10至大约4:1存在。 According to one or more embodiments, the total amount of platinum and palladium in a ratio of the total amount of platinum and palladium from about 1:10 to about 4: 1 is present. 在一个或者多个实施方案中,催化材料可以有效地使先进燃烧柴油发动机排放的HC和CO(包括甲烷组分)氧化,第一洗涂层区活化以用于在与先进燃烧柴油发动机运行相关的高排放和低温条件下使CO和HC氧化。 In one or more embodiments, the catalytic material may be effectively advanced combustion diesel engine emissions of HC and CO (including methane component) oxide, a first washcoat zone associated with activation of the advanced for the combustion of diesel engine operation so that HC and CO oxidation at low temperatures and high emissions.

[0017] 根据一个或者多个实施方案,第一耐火金属氧化物负载体和第二耐火金属氧化物负载体之一或者二者包含氧化铝、二氧化硅、氧化锆、二氧化钛和其组合中的一种或者多种,第二耐火氧化物负载体包含氧化铝、二氧化娃、氧化错、二氧化钛和其组合中的一种或者多种。 [0017] According to one or more embodiments, a first refractory metal oxide support and a second refractory metal oxide support comprises one or both of alumina, silica, zirconia, titania, and combinations thereof one or more of the second refractory oxide support comprises alumina, silica baby, wrong oxidation a titanium dioxide and combinations thereof, or more. 在一个或者多个实施方案中,第一洗涂层和第二洗涂层之一或者二者进一步包含沸石、碱土氧化物、稀土氧化物和贱金属氧化物中的一种或者多种。 In one or more embodiments, one of the first and second washcoat layer washcoat layer further comprises one or both zeolites, alkaline earth oxides, rare earth oxides and base metal oxide or more.

[0018] 在一个或者多个实施方案中,复合物进一步包含基本不含贵族金属组分的底涂层,所述底涂层在第一洗涂层区和第二洗涂层区之一或者二者的下面而涂覆于载体基材。 [0018] In one or more embodiments, the composite further comprises an undercoat layer is substantially free of noble metal component, the undercoat washcoat layer in one of the first and second washcoat zone or region both below and applied to the carrier substrate. 在一个或者多个实施方案中,第一负载包含二氧化铈和含有沸石的分子筛,所述沸石选自β-沸石、ZSM-5或者沸石-Y。 In one or more embodiments, the first load comprising ceria and a zeolite-containing molecular sieve, the zeolite is selected from β- zeolite, ZSM-5 zeolite or -Y. 根据一个或者多个实施方案,催化剂复合物具有大约30g/ft 3至350g/ft3范围的铂和钯总承载量。 According to one or more embodiments, the catalyst composite of about 30g / ft 3 to 350g / total loading of platinum and palladium in the range ft3.

[0019] 本发明的另一个方面涉及处理传统柴油废气流或者先进燃烧柴油废气流的方法。 [0019] Another aspect of the invention relates to a process or method of the conventional art diesel exhaust stream combustion diesel exhaust stream. 方法的一个实施方案包括使废气流通过D0C。 One embodiment of the method comprises passing the exhaust gas stream through D0C. 废气首先通过包含第一洗涂层和第一耐火金属氧化物负载体的第一洗涂层区,所述第一洗涂层含有铂(Pt)和钯(Pd)组分中的一种或者多种。 First by the exhaust gas comprising a first washcoat layer and a first region of the first washcoat layer refractory metal oxide support, wherein the first washcoat layer comprises one component of platinum (Pt) and palladium (Pd), or variety. 接着使废气流通过包含第二洗涂层和第二耐火金属氧化物负载体的第二洗涂层区, 所述第二洗涂层含有多种铂和钯组分中的一种或者多种。 Subsequently the exhaust gas stream through a second washcoat layer comprises a washcoat layer and a second region of the second refractory metal oxide support, said second washcoat layer contains one more components of platinum and palladium or more . 钯组分总量的至少50%位于第一洗涂层区,铂组分总量的至少50%位于第二洗涂层区。 At least 50% of the palladium component located in the first washcoat zone, at least 50% of the total amount of the platinum component in the second washcoat zone.

[0020] 在一个或者多个方法的实施方案中,第二洗涂层基本不含钯。 [0020] In one or more embodiments of the method, the second washcoat layer substantially free of palladium. 在方法的一个或者多个实施方案中,第一洗涂层区延伸至基材的全长并且第二洗涂层区与第一洗涂层区完全重叠。 In one or more embodiments of the method, the first washcoat layer to extend the full length of the substrate region and the second region and the first washcoat layer washcoat completely overlap region. 根据一个或者多个方法的实施方案,第一洗涂层区从入口端延伸至基材长度的大约5%至95%,第二洗涂层区从出口端延伸至基材长度的大约5%至95%。 According to one or more embodiments of the method, the first washcoat zone extending from the inlet end to about 5 to 95% of the length of the substrate, a second washcoat zone extends from the outlet end of the length of the substrate to about 5% to 95%.

[0021] 在一个或者多个方法的实施方案中,第一洗涂层区和第二洗涂层区相互重叠。 [0021] In one or more embodiments of the method, the first washcoat zone and the second washcoat layer overlap region. 在一个或者多个方法的实施方案中,铂和钯以铂与钯的比率从大约1:10至大约4:1存在于整个催化剂复合物中。 In one or more embodiments of the method, the platinum and palladium in a platinum to palladium ratio of from about 1:10 to about 4: 1 is present throughout the catalyst composite.

[0022] 根据一个或者多个方法的实施方案,第一耐火金属氧化物负载体和第二耐火金属氧化物负载体之一或者二者包含氧化铝、二氧化硅、氧化锆、二氧化钛和其组合中的一种或者多种,第二耐火氧化物负载体包含氧化铝、二氧化硅、氧化锆、二氧化钛和其组合中的一种或者多种。 [0022] According to one or more embodiments of the method, one of the first refractory metal oxide support and a second refractory metal oxide support, or both comprises alumina, silica, zirconia, titania, and combinations thereof of one or more of the second refractory oxide support comprises one of alumina, silica, zirconia, titania, and combinations thereof, or more. 在一个或者多个方法的实施方案中,第一洗涂层和第二洗涂层之一或者二者进一步包含沸石、碱土氧化物、稀土氧化物和贱金属氧化物中的一种或者多种。 In one or more embodiments of the method, the first and second wash coat one or both washcoat layer further comprises zeolite, alkaline earth oxides, rare earth oxides and base metal oxide or more of . 根据一个或者多个方法的实施方案,柴油氧化催化剂复合物进一步包含基本不含贵族金属组分的底涂层,所述底涂层在第一洗涂层区和第二洗涂层区之一或者二者的下面而涂覆于载体基材。 The undercoat layer to one or more embodiments of the method, a diesel oxidation catalyst composite further comprises a noble metal component substantially free of the undercoat washcoat layer in the first region and the second region of one washcoat layer or both below and applied to the carrier substrate.

[0023] 在一个或者多个方法的实施方案中,第一负载包含二氧化铈和含有沸石的分子筛,所述沸石选自β-沸石、ZSM-5或者沸石-Y。 [0023] In one or more embodiments of the method, a first load comprising ceria and a zeolite-containing molecular sieve, the zeolite is selected from β- zeolite, ZSM-5 zeolite or -Y. 一个或者多个方法的实施方案可以进一步包含将柴油废气引入位于催化烟灰过滤器(CSF)下游的选择性催化还原(SCR)催化制品中。 One or more embodiments of the method may further comprise the diesel exhaust gas introduced into the catalytic soot filter is located (CSF) downstream of the selective catalytic reduction (SCR) catalyst article. 一个或者多个方法的实施方案可以在与先进燃烧柴油发动机运行相关的高排放和低温条件下使CO和HC氧化。 One or more embodiments of the method may be advanced in the combustion of CO and HC emissions under high and low temperature oxidation conditions related to the operation of the diesel engine.

[0024] 本发明的另一个方面涉及传统柴油或者先进燃烧柴油发动机废气处理系统。 [0024] Another aspect of the invention relates to advanced conventional diesel combustion or diesel engine exhaust gas treatment system. 所述系统包括根据上面任何一个实施方案描述于上面的催化剂复合物类型,以及烟灰过滤器、 催化烟灰过滤器、选择性催化还原(SCR)催化制品和NO x储存和还原(NSR)催化制品中的一种或者多种。 According to one embodiment the system comprises any of the above embodiment to the above described catalyst composite type, and a soot filter, catalyzed soot filter, a selective catalytic reduction (SCR) and the NO x storage catalytic article and reduction (NSR) catalytic article of one or more.

[0025] 附图简述 [0025] BRIEF DESCRIPTION

[0026] 图1是蜂巢型耐火载体元件的透视图,所述元件包含根据本发明的柴油氧化催化(DOC)洗涂层复合物。 [0026] FIG. 1 is a perspective view of a honeycomb-type refractory carrier member, said composite member comprising a washcoat The diesel oxidation catalyst (DOC) of the present invention.

[0027] 图2是相对于图1放大的并沿与图1载体端面平行的平面得到的部分横切面视图, 其显示图1中所示一个气流通道的放大视图。 [0027] FIG. 2 is an enlarged with respect to FIG. 1 and partially cross-sectional view taken along a plane parallel to the end surface of the carrier in FIG. 1, which shows an enlarged view of a gas flow passage shown in FIG.

[0028]图3A至3D显示根据本发明多个实施方案的氧化催化剂复合物的横切面视图。 [0028] Figures 3A to 3D show a cross-section view of a composite oxide catalyst according to various embodiments of the present invention.

[0029] 图4是根据本发明一个实施方案的发动机排放物处理系统的图解。 [0029] FIG. 4 is an illustration of an engine exhaust treatment system in accordance with one embodiment of the present invention.

[0030] 图5是本发明多个实施方案中CO转化的图表。 [0030] FIG. 5 is a graph of a plurality of embodiments of the present invention CO conversion.

[0031]图6是本发明多个实施方案中烃转化的图表。 [0031] FIG. 6 is a graph of a plurality of embodiments of the invention the hydrocarbon conversion.

[0032] 发明详述 [0032] DETAILED DESCRIPTION

[0033] 在描述本发明的几个示例性实施方案之前,将可以理解的是,本发明不限于下面描述中提供的构造或者过程步骤的详述。 [0033] Before describing several exemplary embodiments of the present invention, it will be appreciated that the present invention is not limited to the construction or process steps detailed description provided below. 本发明能够是其他实施方案,并且能够以多种方式实践或者实施。 The present invention is capable of other embodiments and of being practiced or carried out in various ways.

[0034] 本发明的实施方案涉及利用催化剂分区方案,其能够提高Pt/Pd催化剂在柴油发动机应用中特别是先进燃烧应用中的性能。 [0034] The embodiments of the present invention relates to a catalyst partitioning scheme, it is possible to improve the performance of a Pt Pd catalyst is particularly advanced combustion applications / diesel engine applications. 利用新的先进燃烧技术(例如均质充量压燃(HCCI)的柴油发动机通过点火前使发动机气缸内部燃烧火焰的温度降低和增加燃料供给的一致性和混合度,将能够减少排放到发动机外的NO x和颗粒物质(PM)。但是,在将燃烧过程转变为较低的NOx和PM排放的过程中,CO和烃(HC)排放的总量将增加,所形成的HC的性质将发生变化(例如可能产生更多的甲烷),并且废气温度较低。由于这些废气特性对现有柴油排放催化剂系统提出了重大挑战,需要新的催化剂技术,用以符合日益严格的规章制度, 例如Euro 6和US Tier 2Bin 5。 With the new advanced combustion technologies (e.g., homogeneous charge compression ignition (HCCI) diesel engine and the reduction and increase the consistency of the fuel mixture supplied by the internal combustion engine cylinder before ignition of the flame temperature, engine emissions can be reduced to an outer NO x and particulate matter (PM). However, during the combustion process into low emissions of NOx and PM, CO and hydrocarbons (HC) emissions will increase the formed nature of HC will occur change (for example, may produce more methane), and the exhaust gas temperature is low. due to these characteristics existing diesel exhaust emission catalyst system poses a major challenge that requires a new catalyst technology to meet the increasingly stringent regulations, such as Euro 6 and US Tier 2Bin 5.

[0035] 尽管铂(Pt)对于CO和HC具有优良的点燃特性并且是用于去除柴油发动机废气的催化剂复合物中优选的贵金属,最近钯由于其相对较低的成本而引起更大兴趣。 [0035] Although platinum (Pt) for CO and HC and has excellent ignition characteristics of diesel engine exhaust is used to remove the catalyst composite is preferably a noble metal, palladium, recently due to its relatively low cost and cause greater interest. 对于先进燃烧发动机,钯还具有胜于铂的几个性能优势。 For advanced combustion engines, better than platinum-palladium also has several performance advantages. 例如,铂易于被高浓度的CO抑制(即中毒), 并且Pt显示其作为甲烷氧化剂的活性很低。 For example, platinum is easily suppressed high concentrations of CO (i.e. poisoning), and Pt as an active display its low methane oxidizing agent. 然而,钯不被CO自抑制并且已知其比铂对甲烷氧化更有效。 However, since palladium is not known to inhibit the CO and methane oxidation is more effective than platinum. 由于预期先进燃烧柴油发动机排放更多的CO和甲烷,因此使用Pd具有显著益处。 In anticipation of more advanced combustion diesel engine emissions of CO and methane, using Pd thus it has significant benefits.

[0036] 催化剂洗涂层的分区涂覆是本领域技术人员为了提高催化剂在发动机瞬时运行下的性能而经常使用的一项技术。 [0036] The catalyst-coated washcoat partition is a technique for the skilled in the art in order to improve the performance of the catalyst under transient operation of the engine is used regularly. 这通常通过将贵金属复合物和/或贵金属总量分隔至载体基材(例如单片催化剂蜂巢型载体)上的特定位点(或者区)来完成。 This is typically accomplished by site-specific (or regions) the noble metal compound and / or the total amount of noble metal spacer to a carrier substrate (e.g., a honeycomb type monolithic catalyst carrier) on. 此外,分区涂覆使得可以将贱金属氧化物洗涂层材料和其他洗涂层添加剂置于最能增强所负载的贵金属性能的特定位点。 Further, the partition may be coated so that the base metal oxide washcoat materials and other additives washcoat disposed best performance supported noble metal reinforcing a specific site. 较多量的贵金属(具体地是Pt)常常位于载体前段(进口),以达到较快点燃而使CO和HC氧化。 Relatively large amount of noble metal (specifically, Pt) often front section of the carrier (imports) to achieve fast ignition of the CO and HC oxidation. 钯通常位于载体后段(出口),因为载体出口一般由于催化剂点燃因而较热, 而Pd比Pt对热烧结更耐受。 Rear section of the carrier is usually palladium (outlet), generally as the carrier because the catalyst outlet hotter ignition Accordingly, sintering and Pd are more tolerant to heat than Pt. 本发明的实施方案利用催化剂分区方案,通过将较高含量的Pd 置于载体前部区段而将相应较高含量的Pt置于载体后部区段,来增加Pt/Pd制剂在柴油应用中的性能。 Embodiment of the invention using a catalyst partitioning scheme, by a higher level of the Pd onto the carrier and the front section corresponding higher levels of Pt rear section located in the vector, to increase the Pt / Pd formulations diesel applications performance. 该分区方案特别用于消除与先进燃烧柴油发动机相关的高水平CO和HC(特别是甲烷)。 The particular partitioning scheme for eliminating associated with high levels of advanced diesel engines combustion of CO and HC (in particular methane). 由于来源于发动机的高水平CO和HC在经Pd强化的入口区发生反应,在该位置金属位点上所预期的相应较高的局部温度将增加甲烷的氧化,甚至在废气总体温度较低时。 The reaction from the engine due to high levels of CO and HC occur in the inlet region over Pd strengthened, the position of the metal at the site corresponding to the expected higher local temperatures will increase the oxidation of methane, even in the exhaust gas temperature is low overall . 此外,当CO和HC浓度很高时,经较高含量Pd强化的进口在低废气温度下对CO中毒较不敏感。 Further, when CO and HC concentration is high, reinforced by high Pd content importing at a low exhaust gas temperature is not more sensitive to CO poisoning.

[0037] 本发明的分区方案与传统教导相反,其将大部分铂置于更可能发生烧结的载体最热部分。 [0037] The partitioning of the present invention contrary to conventional teachings that most of the hottest portion of the carrier placed in a platinum sintering is more likely to occur. 钯和铂的分区放置使得催化剂组分产生出乎意料地高的CO和HC转化率,甚至在老化之后。 Palladium and platinum partition is placed so that the catalyst component to produce an unexpectedly high conversion of CO and HC, even after aging.

[0038] 本发明多个实施方案的范围包括所有的催化剂洗涂层配方和复合物,其中钯总量的大于大约50%位于载体基材的前部(进口)区段,铂总量的大于大约50%位于后部(出口) 区段。 [0038] scope of the various embodiments of the present invention includes all catalysts and washcoat formulation composite, wherein greater than (inlet) section, the total amount of platinum is greater than about 50% of the total palladium is located in the front portion of the support substrate about 50% at the rear (exit) section. 出乎意料地,不含钯的出口区段显示出最高的CO和HC转化率。 Surprisingly, the palladium-free outlet section showed the highest conversion rates of CO and HC. 更出乎意料地,本发明的实施方案在标准柴油发动机中显示出色的CO和HC转化率。 More unexpectedly, embodiments of the present invention show excellent conversion of CO and HC in the standard diesel engine.

[0039] 在一个或者多个实施方案中,第二区基本不含储氧组分。 [0039] In one or more embodiments, the second region is substantially free of an oxygen storage component. 在一个或者多个实施方案中,第二区基本不含钯。 In one or more embodiments, the second region is substantially free of palladium. 在一个或者多个实施方案中,第一区基本不含分子筛或者沸石。 In one or more embodiments, the first region is substantially free of molecular sieves or zeolites. 在一个或者多个实施方案中,第二区基本不含非沸石的负载贵金属的组分。 In one or more embodiments, the second region is substantially free of non-noble metal components of zeolite. 在一个或者多个实施方案中,第一区和第二区之一或者二者基本不含非贵金属组分。 In one or more embodiments, one of the first and second regions or both substantially free of non-precious metal component. 在一个或者多个实施方案中,柴油氧化催化剂材料基本不含NO x(氮氧化物)储存适宜量的贱金属,所述贱金属包括但不限于Ba、Mg、K和La等。 In one or more embodiments, the diesel oxidation catalyst material is substantially free of NO x (nitrogen oxides) to store a suitable amount of base metal, said base metal including but not limited to Ba, Mg, K and La and the like. 在其他实施方案中,催化材料不含铑。 In other embodiments, the catalytic material is free of rhodium. 在一个或者多个实施方案中,沸石包括沸石、ZSM-5或者沸石-Y。 In one or more embodiments, the zeolite comprises zeolite, ZSM-5 zeolite or -Y.

[0040] 在本发明的特定实施方案中,催化剂复合物、催化剂系统和方法特别适用于处理先进燃烧柴油发动机废气排放物,其特征和不同于传统柴油发动机废气的是其HC和CO排放量较高(在一些情况下高50%至100%)而NO x排放量较低(在一些情况下低2至3倍)。 [0040] In a particular embodiment of the invention, the catalyst composite, a catalyst system and method are particularly applicable to the treatment of advanced diesel engine combustion exhaust emissions, and which is different from the conventional diesel engine exhaust which is an amount of HC and CO emissions than high (in some cases 50 to 100% higher) and lower NO x emissions (2 to 3 times lower in some cases). 同样地,本发明的一个实施方案涉及用于处理先进燃烧柴油发动机废气排放物的氧化催化剂复合物,其包括具有一定长度、入口端和出口端的载体基材,以及载体上的柴油氧化催化剂催化材料,所述柴油氧化催化剂催化材料包括第一洗涂层区和第二洗涂层区。 Similarly, one embodiment of the present invention is directed to an oxidation catalyst for combustion treatment of advanced composite exhaust emissions of diesel engines, comprising a length having inlet and outlet ends of the carrier substrate, a diesel oxidation catalyst and a catalytic material on a carrier the diesel oxidation catalyst comprising a catalytic material washcoat first region and the second washcoat zone. 第一洗涂层区包含第一洗涂层和第一耐火金属氧化物负载体,所述第一洗涂层含有铂(Pt)和钯(Pd)组分中的一种或者多种,并且第一洗涂层区与载体基材的入口端相邻。 The first washcoat layer comprising a first washcoat zone and the first refractory metal oxide support, the first washcoat layer comprises platinum (Pt) and palladium (Pd) or more of one of the components, and the inlet end of the first washcoat zone adjacent the carrier substrate. 第二洗涂层区包含第二洗涂层和第二耐火金属氧化物负载体,所述第二洗涂层含有铂和钯组分中的一种或者多种,并且第二洗涂层区与载体基材的出口端相邻。 The second washcoat layer comprising a second washcoat zone and a second refractory metal oxide support, the second washcoat layer comprises platinum and palladium or more components, and the second washcoat zone adjacent the outlet end of the carrier substrate. 其中钯组分总量的至少50%位于第一洗涂层区,铂组分总量的至少50%位于第二洗涂层区。 Wherein at least 50% of the palladium component located in the first washcoat zone, at least 50% of the total amount of the platinum component in the second washcoat zone.

[0041] 在更具体的实施方案中,第二洗涂层区基本不含钯。 [0041] In a more specific embodiment, the second washcoat zone is substantially free of palladium. 在一个更具体的实施方案中, 第一洗涂层含有Pt和Pd的混合物,并且具有在与先进燃烧发动机运行相关的高排放和低温条件下使CO和HC氧化的活性。 In a more specific embodiment, the first washcoat layer comprising a mixture of Pt and Pd, and has a HC and CO oxidation at low temperatures and high emissions associated with advanced combustion engine operation activity. 第一洗涂层释放的热量可以帮助柴油废气中的甲烷组分发生氧化。 The first washcoat layer of heat release can help in diesel exhaust gas components methane oxidation. 根据一个实施方案,废气中废气组分的燃烧足以产生足以使甲烷组分氧化的局部放热。 According to one embodiment, the combustion exhaust gas components in exhaust gas components sufficient to produce enough methane partial oxidation exotherm. 在具体的实施方案中,第一洗涂层从入口端沿基材上游部分延伸,第二洗涂层区从出口端沿基材下游部分延伸。 In a specific embodiment, the first washcoat layer extending from the inlet end along the upstream portion of the substrate, a second washcoat zone extends from the outlet end of the downstream portion along the substrate.

[0042] 所涉及的催化剂复合物或者催化制品是指包括载体基材(例如蜂巢型基材)的催化制品,其具有含有催化组分的一个或者多个洗涂层,所述催化组分例如能够有效催化HC 和CO氧化的贵金属组分。 [0042] involved in the catalysis or catalyst composite article refers to catalytic article comprising a substrate support (e.g. a honeycomb type substrate) having a catalytic component containing washcoat or more, the catalytic components e.g. It can be a noble metal component effective to catalyze the HC and CO oxidation.

[0043] 所涉及的"基本无"、"基本不含"是指所述材料并非有意提供于所述层中。 [0043] The reference to "substantially none", "substantially free" means that the material is not intentionally provided in said layer. 但是可以领会的是,被认为是微量(即〈材料的10%、9%、8%、7%、%、5%、4%、3%、2%或者甚至1 %)的所述材料可以转移或者扩散至所述层。 It will be appreciated that the trace is considered (i.e., <10% of the material, 9%, 8%, 7%, 5%, 4%, 3%, 2% or even 1%) of the material may or transferred into the diffusion layer.

[0044] 耐火金属氧化物负载体是指孔径大于20A并且孔径分布较宽的负载颗粒。 [0044] The refractory metal oxide support means 20A and pore size greater than the pore size distribution wider particle load. 如本文中所定义,这种金属氧化物负载体不包括分子筛,特别是沸石。 As defined herein, such a metal oxide support does not include a molecular sieve, in particular zeolite. 在特定的实施方案中,可以使用高比表面积耐火金属氧化物负载体,例如氧化铝负载材料,也被称为"γ-氧化铝"或者"活化的氧化铝",其通常显示具有大于每克60平方米的BET表面积("m 2/g"),通常至大约200m2/g或者更高。 In certain embodiments, the use of high specific surface area may be refractory metal oxide support, such as alumina support materials, also referred to as "[gamma] alumina" or "activated alumina", typically exhibit greater than per gram BET surface area of ​​60 square meters ( "m 2 / g"), typically to about 200m2 / g or more. 这种活化的氧化铝一般是γ相和δ相氧化铝的混合物,但是还可以含有大量的η相、κ相和Θ相氧化铝。 Such activated alumina is usually a mixture of γ-phase and δ-phase alumina, but may also contain a large amount of η phase, [kappa] and Θ phase alumina phase. 除活化的氧化铝之外的耐火金属氧化物可以用作特定催化剂中至少某些催化组分的负载。 Refractory metal oxides other than activated alumina may be used as a specific catalyst loading of at least some of the catalytic components. 例如,已知大量的二氧化铈、氧化锆、α-氧化铝和其他材料可以这样使用。 For example, a large number of known ceria, zirconia, alpha] alumina, and other materials may be used as such. 尽管这些材料中很多都具有BET表面积显著低于活化的氧化铝的缺点,但是这一缺点倾向于被所得到的催化剂耐用性更强或者性能增加所抵消。 Although many of these materials have drawbacks alumina BET surface area significantly lower than the activation, but the catalyst durability tends disadvantage being increased or enhanced performance of the resulting offset. "BET表面积"具有通过N2吸附测定表面积的Brunauer、Emmett、Te 11 er方法中所指的一般含义。 "A BET surface area" has the general meaning by Brunauer N2 adsorption surface area measurement Emmett, Te 11 er method referred to. 还可以利用BET型N2 吸附或者解吸实验测定孔直径和孔体积。 Type may also be utilized BET N2 adsorption or desorption experimentally determined pore diameter and pore volume.

[0045] 如本文中所使用,分子筛(例如沸石)是指以微粒形式负载催化性贵族金属的材料,该材料具有基本均一的孔径分布,其平均孔径大小是不大于2〇人。 [0045] As used herein, molecular sieves (e.g., zeolites) refers to a form of particulate catalytic material supported noble metal, the material having a substantially uniform pore size distribution, an average pore size not greater than 2〇 al. 所涉及的催化剂层中"非沸石负载体"是指非分子筛或者非沸石的材料,该材料通过结合、分散、浸渍或者其他适宜方法负载贵金属、稳定剂、促进剂、粘合剂等。 Relates to a catalyst layer in "non-zeolitic load" refers to non-zeolitic molecular sieve material or non, by combining the material, dispersion, impregnation or other suitable methods supported precious metals, stabilizers, promoters, binders and the like. 这种负载体的示例包括但不限于高比表面积耐火金属氧化物。 Examples of such loads include, but are not limited to body high surface area refractory metal oxide. 本发明的一个或者多个实施方案包括包含活化化合物的高比表面积耐火金属氧化物负载体,所述化合物选自以下组:氧化铝、氧化锆、二氧化硅、二氧化钛、二氧化娃-氧化铝、氧化错-氧化铝、二氧化钛-氧化铝、氧化镧-氧化铝、氧化镧-氧化错-氧化铝、氧化钡-氧化铝、氧化钡-氧化镧-氧化铝、氧化钡-氧化镧-氧化钕-氧化铝、氧化错-二氧化硅、二氧化钛-二氧化硅或者氧化锆-二氧化钛。 One or more embodiments of the present invention comprises a high specific surface area activating compound comprising refractory metal oxide support, the compound is selected from the group: alumina, zirconia, silica, titania, silica baby - alumina oxide wrong - alumina, titania - alumina, lanthanum oxide - aluminum oxide, lanthanum oxide - wrong - alumina, barium oxide - aluminum oxide, barium oxide - lanthanum oxide - aluminum oxide, barium oxide - lanthanum oxide - neodymium oxide - aluminum oxide wrong - silica, titania - silica or zirconia - titania.

[0046] 所涉及的"浸渍"是指将含有贵金属的溶液置于材料(例如沸石或者非沸石负载体)的孔中。 [0046] involved "dip" means a hole of a noble metal-containing solution was placed material (e.g. zeolite or non-zeolitic material load) of. 在详述的实施方案中,通过初湿含浸完成贵金属的浸渍,其中含有贵金属的溶液稀释后的体积与负载体的孔体积大致相等。 In detailed embodiments, the noble metal impregnation is completed by incipient wetness, wherein the pore volume of the diluted solution volume containing a noble metal body is substantially equal to the load. 初湿含浸一般使前体溶液基本均一地分布到材料的孔系统中。 Usually incipient wetness precursor solution is substantially uniformly distributed in the pore system of the material. 加入贵金属的其他方法也是本领域已知的并且可以使用。 Other methods are also added to the noble metal known in the art and may be used.

[0047]所涉及的OSC(储氧组分)是指具有多价状态并且能够在氧化条件下与氧化剂(例如氧气或者一氧化二氮)活跃反应或者能够在还原条件下与还原剂(例如一氧化碳(CO)或者氢气)活跃反应的材料。 [0047] OSC (oxygen storage component) involved means a multivalent state and is capable of oxidizing agent (e.g. oxygen or nitrous oxide) or can be active in the reaction with a reducing agent (e.g. carbon monoxide under reducing conditions under oxidizing conditions the reaction of the material (CO) or hydrogen) active. 通常储氧组分包含一种或者多种稀土金属的一种或者多种氧化物。 Typically the oxygen storage component comprises one or more of a rare earth metal oxide or more. 适宜的储氧组分的示例包括二氧化铈、氧化锆和其组合。 Examples of suitable oxygen storage components include ceria, zirconia, and combinations thereof. 氧化镨也可以用作OSC或者促进剂。 Praseodymium oxide can also be used as accelerators or OSC. OSC可以包含一种或者多种促进剂或者改进剂,例如Y、La、Nd、Sm、Pr和其组合。 OSC can comprise one or more promoters or modifiers, e.g. Y, La, Nd, Sm, Pr, and combinations thereof. OSC可以包含于任一层中,特别是在其作为那些层中所含Pd的活性剂的情况下。 OSC may be included in either layer, especially in the case of active agents as those contained in the layer of Pd.

[0048]所涉及的"先进燃烧柴油发动机"与传统柴油发动机不同,包括均质充量压燃(HCCI)、预混合充量压燃(PCCI)和低温燃烧(LTC)发动机,其通过点火前使发动机气缸内部燃烧火焰的温度降低和增加燃料供给的一致性和混合度来运行。 [0048] involved in the "advanced combustion diesel engines" and various conventional diesel engines, comprising a homogeneous charge compression ignition (the HCCI), premixed charge compression ignition (the PCCI) and the low temperature combustion (LTC) of the engine, before ignition by internal combustion engine cylinder and decrease in temperature of the flame and increase the consistency of the fuel mixture supplied to run. 先进燃烧技术的多种变体是本领域已知的,上面所列出的并不意味着包括所有变体。 Advanced combustion technologies many variants are known in the art, listed above is not meant to include all variants. 先进燃烧柴油发动机废气的特征和不同于传统柴油发动机废气的是其与传统柴油发动机相比HC和CO排放量较高(在一些情况下高50%至100%)而NO x排放量较低(在一些情况下低2至3倍)。 Characterized in diesel engine exhaust and combustion advanced Unlike conventional diesel engine exhaust which is compared to traditional diesel engine higher HC and CO emissions (in some cases 50 to 100% higher) and lower NO x emissions ( low 2 to 3 times) in some cases. 更具体地,在新排放驾驶循环(NEDC)中,通常先进燃烧车辆的排放物的特征是含有〈0.18g/km的N0 X、>2.5g/km的CO和>0.5g/km的HC。 More specifically, the new discharge in the driving cycle (the NEDC) usually advanced combustion features of the vehicle emissions containing <0.18g / km of N0 X,> 2.5g / km CO and> 0.5g / km of HC. 在先进燃烧发动机中颗粒物质也显著减少。 It was also significantly reduced in the particulate matter advanced combustion engines. 尽管稀薄燃烧先进燃烧柴油发动机的排放物与火花点火化学计量比汽油发动机的排放物更相似,但是发动机运行模式是完全不同的,因而废气处理方案也是完全不同的。 Although advanced lean-burn combustion emissions diesel engines with spark ignition is more similar to stoichiometric gasoline engine emissions, the engine operating mode is different, and therefore the exhaust gas treating solutions are completely different. 本领域技术人员将领会的是,先进燃烧柴油发动机与传统柴油发动机和汽油火花点火发动机不同,其废气特性和发动机运行模式将需要与以前柴油和火花点火发动机中所用不同的处理方案和/或催化剂复合物,以有效地处理HC、CO和NO x。 Those skilled in the art will appreciate that the advanced combustion diesel engines with conventional diesel engines and gasoline spark ignition different engines, which exhaust gas characteristics and engine operation will require previous diesel and spark ignition engines are different treatment schemes and / or catalyst complex, to effectively deal with HC, CO and NO x.

[0049] 下面根据本发明的实施方案详细描述了废气处理物和系统的组分。 [0049] According to embodiments of the invention below described in detail with the components of the exhaust gas treatment system and the object.

[0050] 载体 [0050] The carrier

[0051] 根据一个或者多个实施方案,载体可以是通常用于制备DOC催化剂的任何材料,优选包含金属或者陶瓷蜂巢型结构。 [0051] According to one or more embodiments, the carrier may be any material commonly used in the preparation of DOC catalyst, preferably comprising a metal or ceramic honeycomb structure. 可以使用任何适宜的载体,例如具有大量细小且平行的气流通道的单片载体,所述通道从载体进口或者出口面延伸穿过,以使通道是开放的,可以使流体流动其中。 Any suitable carrier may be used, for example, a large number of fine parallel gas flow passages of the monolithic carrier, the carrier or from the inlet passage extends through the outlet face, so that the channel is open, the fluid can flow therethrough. 通道从其流体进口至其流体出口基本上是直的通路,其定义为催化材料以"洗涂层"方式涂覆于上面以使流过通道的气体与催化材料相接触的壁。 A fluid passage from the inlet to their fluid outlet, are substantially straight passageway, which is defined as the catalytic material in a "washcoat" so that the above embodiment applied to the wall of the gas flowing through the passages contact the catalytic material. 单片载体的流动通道是薄壁通道,其可以是任何适宜的横切面形状和大小,例如梯形、长方形、正方形、正弦形、六边形、椭圆形、圆环形等。 Monolithic carrier flow channels are thin-walled channels which can be of any suitable cross section shape and size such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular and the like. 这种结构可以在每平方英寸横切面含有大约60至大约600或者更多的气体入口端(即"孔")。 Such structures may contain from about 60 to about 600 or more gas inlet end (i.e., "holes") per square inch in cross-section.

[0052] 陶瓷载体可以由任何适宜的耐火材料制备,例如堇青石、堇青石-α-氧化铝、氮化硅、金刚砂、锆莫来石、锂辉石、硅镁铝合金、硅酸锆石、硅线石、硅酸镁、锆石、透锂长石、α-氧化错、娃酸错等。 [0052] The ceramic carrier may be prepared by any suitable refractory material made, such as cordierite, cordierite -α- alumina, silicon nitride, silicon carbide, zircon mullite, spodumene, attapulgite aluminum silicate, zircon , sillimanite, magnesium silicates, zircon, petalite, alpha] oxide wrong, the wrong baby acid and the like.

[0053] 用于本发明中分层催化剂复合物的载体还可以是金属性质的,可以非金属包含一种或多种金属或者金属合金。 [0053] The present invention is a vector layered catalyst composite may also be metallic in nature, it may comprise one or more non-metal metal or metal alloy. 可以使用多种形状的金属载体,例如波纹状薄片或者单片形式。 It may be used various shapes of the metal support, such as corrugated sheet or monolithic form. 适宜的金属负载体包括耐热金属和金属合金,例如钛和不锈钢以及含有大量铁或者以铁作为主要组分的其他合金。 Suitable metal loadings include the heat resistant metals and metal alloys such as titanium and stainless steel and other alloys containing a large amount of iron or iron as a main component. 这种合金可以含有镍、铬和/或铝中的一种或者多种,并且这些金属的总量有利地包含至少15重量%的合金,例如10-25重量%的铬、3-8重量%的铝和至多20重量%的镍。 Such alloys may contain nickel, chromium and / or one or more of aluminum, and the total amount of these metals is advantageously comprises at least 15 wt% of the alloy, e.g., 10-25 wt% chromium, 3-8 wt% aluminum and up to 20% by weight of nickel. 合金可以含有少量或者微量的一种或者多种其他金属,例如猛、铜、隹凡、 钛等。 Alloys may contain little or trace amounts of one or more other metals, e.g. Meng, copper, where the short-tailed, and titanium. 表面或者金属载体可以于高温(例如l〇〇〇°C或者更高)氧化,以通过在载体表面形成氧化物层来提高合金的耐腐蚀性。 Metal surface or carrier may be a high temperature (e.g. l〇〇〇 ° C or higher) oxide, in order to improve the corrosion resistance of the alloy by forming an oxide layer on the surface of the support. 这种高温诱导的氧化可以增强耐火金属氧化物负载体和促进催化的金属组分与载体的粘合。 Such high temperature-induced oxidation may enhance the refractory metal oxide support and promote adhesion of the metal components of the catalytic support.

[0054]催化剂复合物的制备 Preparation of the catalyst composite [0054]

[0055]可以使本发明的催化剂复合物形成单层或者多层。 [0055] The catalyst composite can be formed according to the present invention, a single layer or a multilayer. 在一些情况下,适合制备催化材料的浆料,并且利用该浆料在载体上形成多层。 In some cases, the catalytic material prepared for the slurry, and the slurry is formed using a plurality of layers on the support. 可以通过熟知的过程容易地制备复合物。 Complexes can be readily prepared by processes well known. 下面阐述了一种代表性过程。 The following describes a representative procedure. 本文中使用的术语"洗涂层"具有本领域的一般含义,是指涂覆于基材载体材料上的催化材料或者其他材料的薄附着洗涂层,所述基材载体材料例如蜂巢型载体元件,其足够多孔以允许待处理的气流穿过通道。 Used herein, the term "washcoat" has a general meaning in the art, refers to a thin coating adhered to a substrate carrier material, or other catalytic material washcoat material, the substrate material such as a honeycomb-type carrier support element, which is sufficiently porous to allow gas flow through the passage to be treated.

[0056]可以在单片载体上容易地制备催化剂复合物层。 [0056] The catalyst composite can be readily prepared in layers on a monolithic carrier. 对于特定洗涂层的第一层,在适宜的介质(例如水)中将高比表面积耐火金属氧化物(例如γ -氧化铝)的磨碎颗粒制成浆料。 A first washcoat for a particular layer in a suitable medium (e.g., water) in the high surface area refractory metal oxide (e.g., γ - alumina) was slurried milled particles. 接着使载体在这种浆料中浸蘸一次或多次或者将浆料涂覆于载体上,以使所需量的金属氧化物沉积于载体上,例如每次大约浸蘸大约0.5至大约2.5g/in 3。 The carrier is then dipped in this slurry one or more times, or the slurry applied to the carrier, so that the desired amount of metal oxide deposited on a support, for example, dipping each about about 0.5 to about 2.5 g / in 3. 为了使组分(例如贵金属(例如钯、铑、铂和/或其组合)和稳定剂和/或促进剂)融合,可以在涂覆于载体之前将这些组分以水溶性或者水分散性化合物或者复合物的混合物形式融合于浆料中。 To the components (e.g., noble metals (e.g. palladium, rhodium, platinum, and / or combinations thereof) and a stabilizer and / or promoter) fused to a carrier may be applied before these components soluble or water-dispersible compound or a composite form of a mixture in the slurry is fused. 其后通过加热对经涂层的载体进行煅烧,例如于400-600°C进行大约10分钟至大约3小时。 Thereafter calcined carrier by coating by heating, for example at 400-600 ° C for about 10 minutes to about 3 hours. 通常当需要使用钯时,使用化合物或者复合物形式的钯组分,以使组分分散于耐火金属氧化物负载体(例如活化的氧化铝)上。 It is normally required to use palladium compound or complex used in the form of palladium component dispersed on the components to (e.g. activated alumina) a refractory metal oxide support. 为了本发明的目的,术语"钯组分"是指煅烧后或者使用时分解或者转化成催化活性形式的任何化合物、复合物或者类似,一般是金属或者金属氧化物。 For purposes of this invention, the term "palladium component" means any compound, complex decomposition or converted into a catalytically active form when used, or after calcination, or the like, typically metal or metal oxide. 可以使用金属组分的水溶性化合物或者水分散性化合物或者复合物,只要用于浸渍或者使金属组分沉积于耐火金属氧化物负载体颗粒上的液体介质与金属或者其化合物或者其复合物或者存在于催化剂复合物中并且能够通过加热后和/或在真空应用中挥发或者分解从金属组分中去除的其他组分不会发生可逆反应。 Metal component may be used water-soluble compounds or water-dispersible compound or complex, as long as the metal components used for the impregnation or deposited on a refractory metal oxide support on the liquid medium and the metal particles, or a compound or complex, or present in the catalyst composite and the rear through heat and / or other volatile or decomposing from the metal components removed in vacuo and the application component is not reversible reactions occur. 在一些情况下,直至催化剂投入使用并且在运行中遇到高温时才能完成液体的去除。 In some cases, until the catalyst is placed into use and to complete the removal of the liquid when the high temperatures encountered during operation. 一般地,从经济学和环境方面的角度来看,可以使用贵金属可溶性化合物或者复合物的水溶液。 Generally, from an economic and environmental point of view, it may be used an aqueous solution of a soluble noble metal compound or complex. 适宜的化合物的非限定性示例包括硝酸钯、 四氨合硝酸钯、氯化铂和硝酸铂。 Non-limiting examples of suitable compounds include palladium nitrate, tetraammine palladium nitrate, platinum nitrate and platinum chloride. 在煅烧步骤中或者至少在使用复合物的初期,这种化合物转化成金属或者其化合物的催化活性形式。 In the calcination step, or at least in the initial use of the composite, such compounds are converted into a catalytically active form of the metal or a compound thereof.

[0057]制备本发明中分层催化剂复合物任一层的一种适宜方法是制备所需贵金属化合物(例如钯化合物)的混合溶液和至少一种负载体,所述负载体例如磨碎的高比表面积耐火金属氧化物负载体(例如γ -氧化铝),其足够干燥,能够吸收基本所有的溶液以形成湿润固体,所述湿润固体随后与水混合以形成可洗涂层的浆料。 [0057] A suitable method for the preparation of the present invention in a layered catalyst composite according to any one of the preparation of the desired noble metal compound (e.g. palladium compound) mixed solution thereof and at least one load, the load of the body is high, for example, ground the specific surface area refractory metal oxide support (e.g. γ - alumina), which is sufficiently dried, is capable of absorbing substantially all of the solution to form a wet solid, the solid was then wet mixed with water to form a washcoat slurry. 在一个或者多个实施方案中,浆料是酸性的,具有例如大约2至小于大约7的pH值。 In one or more embodiments, the slurry is acidic, having for example a pH of from about 2 to about less than 7. 可以通过将足够量的无机酸或者有机酸加入浆料中使浆料的PH值降低。 It can be reduced by a sufficient amount of an inorganic or organic acids to the slurry the slurry PH value manipulation. 当考虑了酸与原料的相容性时,可以使用二者的组合。 When considering the compatibility of the acid with the raw material, a combination of both. 无机酸包括但不限于硝酸。 Inorganic acids include but are not limited to, nitric acid. 有机酸包括但不限于乙酸、丙酸、草酸、丙二酸、丁二酸、谷氨酸、己二酸、马来酸、富马酸、邻苯二甲酸、酒石酸、柠檬酸等。 Organic acids include but are not limited to, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, glutamic acid, adipic acid, maleic acid, fumaric acid, phthalic acid, tartaric acid, citric acid and the like. 之后如果需要,将水溶性或者水分散性化合物和/或稳定剂(例如乙酸钡)和促进剂(例如硝酸镧)加入浆料中。 Then, if desired, be added to the slurry a water-soluble or water-dispersible compound, and / or stabilizers (e.g., barium acetate) and a promoter (e.g., lanthanum nitrate).

[0058]在一个实施方案中,之后将浆料研磨,以使基本上所有固体具有平均直径小于大约20微米的颗粒大小,即在大约0.1-15微米之间。 [0058] In one embodiment, the slurry after grinding, so that substantially all of the solids having an average diameter of less than about 20 microns particle size, i.e., about 0.1 to 15 microns between. 可以在球磨机或者其他类似的设备中进行研磨,并且浆料的固体含量可以是例如大约20-60重量%,更具体地是大约30-40重量%。 It may be performed in a ball mill or other similar equipment triturated, and the solid content of the slurry may be, for example, about 20-60 wt%, more specifically from about 30-40% by weight.

[0059] 可以利用与上面描述的在载体上沉积第一层的相同方法在第一层上制备和沉积附加层,即第二层和第三层。 [0059] The additional layers may be utilized and deposited on the first layer was prepared in the same manner as the first layer is deposited on the support as described above, i.e., the second and third layers.

[0060] 洗涂层后,可以利用本领域已知的方法制备分区催化剂基材,例如如第7,189,376 号美国专利中所描述,其作为整体通过引用并入本文。 [0060] After washing the coating, the partition may be prepared using the present catalyst base material known in the art, such as U.S. Patent No. 7,189,376 described, which is incorporated herein by reference in its entirety.

[0061] 如上面所指出,最近钯(Pd)由于其相对较低的成本开始引起更大兴趣。 [0061] As noted above, recent palladium (Pd) due to its relatively low cost begun to attract greater interest. 但是,成本不是设计汽车用催化剂复合物时需要考虑的唯一因素。 However, cost is not the only factor in automotive catalyst complex design needs to be considered. 不论成本大小,如果特定的催化剂材料在特定的发动机废气环境中易于中毒或者降解,那么如果催化剂复合物随着时间将会中毒或者降解则在催化剂复合物中将不使用该特定材料。 Regardless of the size of the cost, if a specific catalyst poisoning material is liable to specific environment or the degradation of engine exhaust gas, then if poisoned catalyst composite will degrade over time or the particular material is not used in the catalyst composite. 在与先进燃烧柴油发动机相关的实施方案中,Pd具有胜于铂的几个性能优势。 In embodiments associated with advanced combustion diesel engine, Pd better than platinum has several performance advantages. 例如,铂易于被高浓度的CO抑制(即中毒),并且Pt使甲烷氧化的能力很低。 For example, platinum is easily suppressed high concentrations of CO (i.e. poisoning), and the ability to make low methane oxidation of Pt. 另一方面,Pd不被CO自抑制并且已知其比铂对甲烷氧化更有效。 On the other hand, Pd is not from CO and is known to inhibit the oxidation of methane is more effective than platinum. 由于预期先进燃烧柴油发动机排放更多的CO和甲烷,因此使用Pd具有显著益处。 In anticipation of more advanced combustion diesel engine emissions of CO and methane, using Pd thus it has significant benefits.

[0062] 由于在冷启动条件下的燃烧特性不稳定,先进燃烧发动机可能将在常规模式下启动,这产生较少的CO和HC排放物。 [0062] Because the combustion characteristics of the cold start condition is unstable, advanced combustion engine may be started in the normal mode, which produce less CO and HC emissions. 发动机尽快(例如1-2分钟后)进入"先进燃烧模式",以减少排放到发动机外的NO x和PM。 As soon as the engine (e.g., 1-2 minutes) into the "advanced combustion mode", in order to reduce emissions to the outside of the engine NO x and PM. 催化剂必须在两种运行模式下保持活性,并且因而能够最大限度地处理CO和HC排放物。 The catalyst activity must be maintained in both modes of operation, and it is possible to maximize the processing of a CO and HC emissions. 尽管基于Pt或者Pt/Pd的常规催化剂在常规柴油运行条件下显示出处理CO和HC的优良性能,其点燃温度在排放到发动机外的CO和HC水平较高时显著提高。 Although conventional catalysts based on Pt or Pt / Pd exhibits excellent process of CO and HC performance under normal operating conditions of diesel, its ignition temperature significantly increased when discharged to the outside of the engine high CO and HC levels. 此外,一旦催化剂被活化并且在"先进燃烧模式"中发挥功能,其一定能够有效地使这些组分氧化,甚至随着发动机外的总体温度下降。 Further, once the catalyst is activated and functions in the "advanced combustion mode" in which certain of these components can be efficiently oxidized even as the overall temperature of the outside of the engine decreases.

[0063] 参考图1和图2更容易理解根据本发明的一个或者多个实施方案的催化剂复合物。 [0063] Referring to Figures 1 and 2 more readily appreciated from the catalyst composite of the present invention in accordance with one or more embodiments. 图1和2根据本发明的一个实施方案显示耐火载体元件2。 Figures 1 and 2 show a refractory support element 2 according to an embodiment of the present invention. 参考图1,耐火载体元件2是圆柱形的,其具有圆柱形外表面4、上游端面6和与端面6相同的下游端面8。 Referring to Figure 1, refractory support element 2 is cylindrical, having a cylindrical outer surface 4, the same downstream end face 6 and the upstream end face 6 and the end face 8. 载体元件2具有形成于其中的大量细小且平行的气流通道10。 2 is formed on the carrier element having a large number of fine, parallel gas flow passages 10 therein. 如图2中所见,气流通道10由壁12形成,并且从上游端面6在载体2中延伸至下游端面8,通道10是畅通的,以允许流体(例如气流)通过气流通道10纵向地流过载体2。 As seen in Figure 2, the gas flow passage 10 formed by the wall 12, and extends from the upstream end face 6 on carrier 2 to the downstream end 8, the channel 10 is smooth to allow fluid (e.g., air flow) 10 longitudinally through the air flow passage over 2 carrier. 如图2中更易看到的,壁12的尺寸和设置使得气流通道10具有基本规则的多边形形状,在描述的实施方案中基本是正方形的,但是依照JCDettling等于1982 年6月15日授权的第4,335,023号美国专利具有圆角。 More visible in FIG. 2, the wall 12 is sized and disposed such that the gas flow passage having a substantially regular polygonal shape 10, in the embodiment described is substantially square, but in accordance with JCDettling equal to 15 June 1982 authorization of U.S. Patent No. 4,335,023 having rounded corners. 在本领域和下面一些情况下被称为"洗涂层"的第一洗涂层14附着于载体元件的壁12或者涂覆于其上。 A first washcoat layer in this art and the following are some cases referred to as "washcoat" is attached to the support member 14 of wall 12 or coated thereon. 如图2中所显示,第二洗涂层16涂覆于如上面所描述的第一洗涂层14上。 Shown in FIG. 2, the second washcoat layer applied to the first washcoat layer 16 as described above on 14. 在一个实施方案中,可以将底涂层(未显示)涂于基材第一洗涂层16的下面。 In one embodiment, the undercoat layer may be (not shown) applied to the substrate below the first wash coat layer 16.

[0064]如图2中所显示,载体元件包括气流通道10形成的空隙空间,并且这些通道10的横切面区域和限定通道的壁12的厚度在一种载体元件类型中和在另一种中不同。 [0064] The display shown in Figure 2, the carrier element includes a void space 10 formed by the gas flow passage, and the thickness of the wall cross-section area of ​​the channels 10 and 12 define a channel in a carrier member and in the other type of different. 类似的,载体上涂覆的洗涂层的重量在不同情况下变化。 Similarly, the carrier coated washcoat weight change under different circumstances. 因此,在描述洗涂层或者催化金属组分或者复合物中其他组分的量时,使用每单位体积的催化剂载体上的组分重量单位是便利的。 Accordingly, in describing the washcoat or catalytic amounts of metal components or other components of the composite, a component on the basis weight per unit volume of the catalyst support is facilitated. 因此,本文中使用的单位克每立方英寸("g/in 3")和克每立方英尺("g/ft3")是指每体积载体元件(包括载体元件中空隙空间的体积)的组分重量。 Thus, as used herein units grams per cubic inch ( "g / in 3") and grams per cubic foot ( "g / ft3") refers to a component per volume of the carrier element (carrier element comprises a void space volume) of weight.

[0065]在另一个实施方案中,本发明的洗涂层可以分区涂覆,其中第一洗涂层在载体基材的上游端,第二洗涂层在载体基材的下游端。 [0065] In another embodiment, the washcoat coating according to the present invention can be partitioned, wherein the first washcoat layer at the upstream end of the carrier substrate, the carrier substrate at the downstream end of the second washcoat layer. 例如,上游洗涂层可以覆盖基材上游区段, 而下游洗涂层可以覆盖基材下游区段。 For example, the upstream washcoat layer may cover the substrate upstream segment and the downstream segment downstream washcoat may cover the substrate. 在这种实施方案中,本发明的第二洗涂层或者下游洗涂层可以至少部分地覆盖第一洗涂层或者上游洗涂层。 In such embodiments, the second washcoat layer of the present invention or a downstream washcoat layer may be at least partially cover the first upstream washcoat layer or washcoat.

[0066]参考图3A至3D可以更容易地理解包含上游区和下游区的催化剂复合物实施方案。 [0066] 3A to 3D may be more readily understood by comprising an upstream region and a downstream region of the catalyst composite embodiment. 图3A显示用于去除发动机废气排放物的分区氧化催化剂复合物20的一个实施方案。 3A shows one embodiment for removing an oxidation catalyst composite partition engine exhaust emissions 20. 载体基材22包含两个分离的分区涂覆的洗涂层,所述载体基材例如蜂巢型单片,其具有入口端或者上游端25、出口端或者下游端27以及在入口端25和出口端之间延伸的轴长。 22 comprises two separate carrier substrate coated washcoat partitions, said carrier substrate such as a monolithic honeycomb type, having an inlet end or upstream end 25, a downstream end or outlet end and the inlet end 27 and an outlet 25 extending between the ends of the long axis. 第一洗涂层24和第二洗涂层26涂覆于基材22。 The first washcoat and the second washcoat layer 24 applied to a substrate 26 22. 第一洗涂层24从入口端或者上游端25延伸,其中含有第一耐火金属氧化物负载体,所述负载包含铂(Pt)组分和钯(Pd)组分中的一种或者多种。 The first washcoat layer 24 extending from the inlet end 25 or upstream end of which comprises a first refractory metal oxide support, said load comprising platinum (Pt) component and one component of palladium (Pd) or more . 第二洗涂层26从出口端或者下游端27延伸,其中含有第二耐火金属氧化物负载体,所述负载体包含铂(Pt)组分和钯(Pd)组分中的一种或者多种。 The second washcoat layer 26 extends from the outlet end, or downstream end 27, the second containing the refractory metal oxide support, the load comprises one component of platinum (Pt) component, and palladium (Pd) or multiple species. 在图3A所显示的实施方案中,第二洗涂层区26至少部分地与第一洗涂层区24重叠。 In the embodiment shown in FIG. 3A, the second washcoat layer region 26 at least partially overlaps the first washcoat zone 24. 催化剂复合物在第一洗涂层区24中含有全部钯组分的至少大约50%,在第二洗涂层区26中含有铂组分的至少大约50%。 All catalyst composite comprising palladium component, at least about 50% of the washcoat layer in the first region 24, region 26 in the second washcoat layer containing a platinum component, at least about 50%. 在一个详述的实施方案中,第二洗涂层基本不含钯。 In a detailed embodiment, the second washcoat layer substantially free of palladium.

[0067]在一些特定的实施方案中,第一洗涂层区24覆盖基材22的全长,第二洗涂层区26 覆盖基材22的部分长度。 [0067] In some particular embodiments, the first washcoat zone 24 covers the entire length of base member 22, a second washcoat layer 26 covers part of the length of the substrate region 22. 在其他特定的实施方案中,第一洗涂层区24覆盖基材22的部分长度,第二洗涂层区26覆盖基材22的全长。 In other specific embodiments, the first washcoat layer 24 covers part of the length of the substrate region 22, a second washcoat zone 26 covers the entire length of the substrate 22. 第一洗涂层区24或者第二洗涂层区26均可以首先涂覆于基材22上,另一洗涂层与其重叠或者相接触。 The first region 24 or the second washcoat zone washcoat layer 26 can be first coated onto a substrate 22, a further washcoat overlap or contact therewith.

[0068]上游洗涂层区24的长度还可以用催化元件上游至下游边缘长度的百分比来描述。 [0068] The length of the upstream washcoat zone 24 may also be a percentage of the length of the downstream edge of the upstream catalytic element used to be described. 通常上游洗涂层区24包括基材负载22总长度的大约5%至大约95%。 Typically the upstream washcoat layer 24 comprises a region of about 5% to about 95% of the total length of the base load 22. 还示例了上游洗涂层区24达到基材22长度的大约20%、大约40%和大约60%。 Also the upstream washcoat sample region 24 up to about 20% of the length of the base 22, about 40% and about 60%. 下游洗涂层区26覆盖基材22剩余下游部分。 Region downstream washcoat portion 26 covering the remaining downstream of the substrate 22. 因此,下游洗涂层区26可以包括基材22轴长的95%至大约5%。 Thus, the downstream washcoat zone 26 may comprise an axial length of 22 to 95% about 5% of the substrate.

[0069]根据其他实施方案,如图3B中所显示,底涂层28可以先于第一洗涂层区24或者第二洗涂层区26而涂覆于基材上,无论首先涂覆哪个洗涂层区。 [0069] According to another embodiment, shown in Figure 3B, the undercoat layer 28 may first washcoat layer 24 or the second region to the first region washcoat layer 26 is coated on the substrate, regardless of which first coated wash coating area. 在一个特定的实施方案中,底涂层不含有意添加到底涂层复合物中的贵金属组分。 In a specific embodiment, the undercoat layer is free of intentionally added precious metal component in the end of the coating compound. 例如,底涂层可以包含耐火金属氧化物负载体。 For example, the undercoat layer may comprise a refractory metal oxide support. 通过扩散或者迀移,底涂层层28中可以存在第一洗涂层中的一些钯或者铂。 Gan diffuse or move through the undercoating layer 28, a palladium or platinum may be present in some of the first washcoat layer. 第一洗涂层区24和第二洗涂层区26的组合可以如上面根据图3A所描述。 The first region 24 and the second washcoat zone composition washcoat layer 26 may be as described above according to FIG. 3A.

[0070] 参考图3C,显示了一个可选的洗涂层方案。 [0070] Referring to Figure 3C, show an alternative embodiment of the washcoat. 在该实施方案中,第一洗涂层区24从入口端向出口端延伸。 In this embodiment, the first washcoat zone 24 extends from the inlet end to the outlet end. 第二洗涂层区26与第一洗涂层区相邻并位于其下游。 The second washcoat layer region 26 adjacent to the first washcoat zone and downstream. 第一洗涂层区24 可以至少部分地与第二洗涂层区重叠。 The first washcoat layer region 24 can be at least partially overlap the second washcoat zone. 在一个实施方案中,第一洗涂层区24包含第一耐火金属氧化物负载体,所述负载包含铂和钯组分中的至少一种。 In one embodiment, the first washcoat layer comprises a first region 24 a refractory metal oxide support, said load comprising at least one of platinum and palladium components. 第二洗涂层区26包含第二耐火氧化物负载体以及铂和钯组分中的至少一种。 The second washcoat layer comprises a second region 26 the refractory oxide support and at least one component of platinum and palladium. 在一个详述的实施方案中,铂总量与钯总量的比率在大约10:1至大约1:4、4:1至大约1:10或者1:4至大约4:1之间。 In a detailed embodiment, the ratio of the total amount of platinum and palladium is between about 10: 1: 1 to about 1: 4, 4: 1 to about 1:10, or 1: 4 to about 4. 该比率还可以在大约3:1至大约1:3、大约2:1至大约1:2和大约1:1的范围内。 This ratio can also be from about 3: 1 to about 1: 3, about 2: 1 range: 1 to about 1: 2 and about 1. 第一洗涂层区可以从入口端25 延伸至基材22轴长的大约5%至大约95%。 A first washcoat zone may extend from the inlet end 25 to the axial length of the substrate 22 is from about 5% to about 95%. 第二洗涂层区26从出口端27延伸,并且第二洗涂层区26可以从基材22轴长的大约5%至大约95%延伸。 The second washcoat layer region 26 extends from the outlet end 27, and a second washcoat layer 26 may extend from the region 22 of the axial length of about 5% to about 95% of the substrate.

[0071] 图3D显示第一洗涂层区24和第二洗涂层区26沿载体基材22的长度并排定位的一个实施方案。 [0071] FIG. 3D shows an embodiment of a first length 22 is positioned side by side region 24 and the second washcoat zone washcoat layer 26 along the carrier substrate. 特定实施方案的第一洗涂层区24从基材22的入口端25延伸至基材22长度的大约5%至大约95%。 A first washcoat zone particular embodiment extends from the inlet end 24 of the base 25 to 22 base length 22 is from about 5% to about 95%. 第二洗涂层区26从基材22的出口端27延伸基材轴长的大约5%至大约95%。 The second washcoat layer base region 26 extending long axis of about 5% to about 95% from the outlet end 22 of the base 27. 第一洗涂层和第二洗涂层的组合可以如上面根据图3A至3C所描述。 The first washcoat and the second washcoat composition can be as described above in accordance with FIGS. 3A to 3C.

[0072] 第一洗涂层和第二洗涂层中组分的承载量如下。 [0072] The carrying amount of the first washcoat and the second washcoat components in the following.

[0073]第一洗涂层中Pd组分可以以大约10g/ft3至200g/ft3范围的量存在(包括20、30、 40、50、60、70、80、90、100、110、120、130、140、150、160、170、180和19(^/代3)。?七组分可以以大约l〇g/ft3 至140g/ft3 范围的量存在(包括20、30、40、50、60、70、80、90、100、110、120、 130g/ft3)。在一些方面中钯和铂的总承载量是大约20g/ft 3至400g/ft3的范围(包括30、40、 50、60、70、80、90、100、110、120、130、140、150、160、170、180、190、200、210、220、230、240、 250、260、270、280、290、300、310、320、330、340、350、360、370、38(^P390g/ft 3)。 [0073] The first component may be of Pd washcoat / ft3 amount present in the range of about 10g / ft3 to 200 g of (including 20, 30, 40,50,60,70,80,90,100,110,120, 130,140,150,160,170,180 and 19 (^ / substituting 3).? seven components may be present in an amount of about ft3 range l〇g / ft3 to 140 g of / (including 20,30,40,50, 60,70,80,90,100,110,120, 130g / ft3). in some aspects, the total loading of platinum and palladium is about 20g / ft 3 range to 400g ft3 / (including 30, 40, 50, 60,70,80,90,100,110,120,130,140,150,160,170,180,190,200,210,220,230,240, 250,260,270,280,290,300, 310,320,330,340,350,360,370,38 (^ P390g / ft 3).

[0074]耐火氧化物负载体(例如氧化铝)可以以大约0.1至大约3g/in3的范围存在,更具体的范围是大约0.5至大约2 g/ i η3。 [0074] The refractory oxide support (e.g. alumina) may range from about 0.1 to about 3g / in3 is present, more particularly in the range of about 0.5 to about 2 g / i η3. 分子筛(例如Η-β-沸石)可以以大约0.1至大约lg/in3的范围存在,更具体的范围是大约0.2至大约0.5g/in 3。 Molecular sieves (e.g. zeolite Η-β-) may range from about 0.1 to about lg / in3 is present, more particularly in the range of about 0.2 to about 0.5g / in 3. 多个实施方案中第一洗涂层和/或第二洗涂层的负载进一步包含沸石、碱土氧化物、稀土氧化物和贱金属氧化物中的一种或者多种。 A first plurality of embodiments washcoat or load and / or the second washcoat layer further comprises zeolite, alkaline earth oxides, rare earth oxides and base metal oxide or more. 在其他详述的实施方案中,所述负载体进一步包含二氧化铈和分子筛,所述分子筛包含选自β-沸石、ZSM-5或者沸石-Y的沸石。 In other detailed embodiments, the body further comprises a load ceria and a molecular sieve comprises a zeolite selected from β- zeolite, ZSM-5 zeolite or a -Y.

[0075]本发明的柴油氧化催化剂(DOC)复合物可以用于包含一种或者多种附加成分的集成排放物处理系统中,以处理柴油废气排放物。 Diesel Oxidation Catalyst [0075] the present invention (DOC) may be used for complex integrated emission treatment system comprising one or more additional ingredients, to treat diesel exhaust emissions. 例如,排放物处理系统可以进一步包含烟灰过滤器组分和/或选择性催化还原(SCR)催化制品。 For example, the emission treatment system may further comprise soot filter component and / or selective catalytic reduction (SCR) catalytic article. 柴油氧化催化剂可以位于烟灰过滤器和/或选择性催化还原组分的上游或者下游。 A diesel oxidation catalyst and a soot filter may be located upstream or downstream / or selective catalytic reduction component.

[0076]除了利用氧化催化剂处理废气排放物之外,本发明还利用烟灰过滤器去除颗粒物质。 [0076] In addition to process emissions by the oxidation catalyst addition, the present invention also utilizes soot filter to remove particulate matter. 烟灰过滤器可以位于DOC上游或者下游,但是烟灰过滤器通常位于柴油氧化催化剂下游。 Soot filter may be located upstream or downstream of the DOC, the soot filter is typically located downstream of the diesel oxidation catalyst. 在一个实施方案中,烟灰过滤器是催化烟灰过滤器(CSF) XSF可以包含涂有洗涂层的基材,所述洗涂层含有用于烧掉所捕获的烟灰和/或者使废气流排放物氧化的一种或者多种催化剂。 In one embodiment, the soot filter is a catalyzed soot filter (CSF) XSF may comprise a substrate coated with a washcoat, the washcoat comprising a burn soot captured and / or flow of the exhaust gas emission one kind or more oxidation catalysts. 一般地,烟灰燃烧催化剂可以是用于燃烧烟灰的任何已知的催化剂。 Generally, the soot combustion catalyst may be any of the known catalysts for soot combustion. 例如,CSF可以涂有用于使未燃烃和一定程度上使颗粒物质燃烧的一种或者多种高比表面积耐火氧化物(例如氧化铝或者二氧化铈-氧化锆)。 For example, CSF may be coated with a unburned particulate matter combustion of one or more high specific surface area refractory oxide and hydrocarbons to some extent (e.g., alumina, or ceria - zirconia). 烟灰燃烧催化剂可以是包含一种或者多种贵金属(PM)催化剂(铂、钯和/或铑)的氧化催化剂。 Soot combustion catalyst may comprise one or more precious metal (PM) catalysts (platinum, palladium and / or rhodium) is an oxidation catalyst.

[0077] 一般地,可以使用本领域任何已知的过滤器基材,包括例如蜂巢型壁流式过滤器、 线绕式或者填充式纤维过滤器、开孔泡沫、烧结金属过滤器等,优选使用壁流式过滤器。 [0077] Generally, any known filter substrate of the present art, including for example, honeycomb-type wall flow filter, wirewound or filled type fiber filters, open cell foams, sintered metal filters, etc., preferably using the wall-flow filter. 用于负载CSF复合物的壁流式基材具有沿基材纵轴延伸的细小且基本上平行的气流通道。 For wall flow substrates have a load CSF composite fine and substantially parallel gas flow passages extending along the longitudinal axis of the substrate. 通常每个通道在基材体的一端封闭,与其交错的通道在相反端面封闭。 Typically, each channel at one end of the base body is closed, its closed channel interleaved counter-face. 这种单片载体可以含有横切面每平方英寸大约700或者更多的气流通道(或者"孔"),尽管可以使用少得多的数量。 Such monolithic carriers may contain cross-section per square inch to about 700 or more flow passages (or "holes"), although much smaller number may be used. 例如,载体可以具有每平方英寸大约7至600、更通常大约100至400个孔("cpsi")。 For example, the carrier may have per square inch of about 7-600, more typically about 100 to 400 cells ( "cpsi"). 孔的横切面可以是长方形、正方形、圆环形、椭圆形、三角形、六边形或者是其他多边形。 Cross-section hole may be rectangular, square, circular, oval, triangular, hexagonal or other polygonal shapes. 壁流式基材通常具有〇. 002和0.1英寸之间的厚度。 Wall flow substrates typically have a square. The thickness of between 002 and 0.1 inches. 优选壁流式基材具有0.002和0.015英寸之间的厚度。 Preferred wall flow substrates have a thickness of between 0.002 and 0.015 inches.

[0078]通常壁流式过滤器基材由陶瓷样材料构成,例如堇青石、α-氧化铝、金钢砂、氮化硅、氧化锆、莫来石、锂辉石、硅镁铝合金或者硅酸锆石,或者多孔的耐火金属。 [0078] typically wall flow filter substrate composed of ceramic-like materials such as cordierite, alpha] alumina, corundum, silicon nitride, zirconia, mullite, spodumene, aluminum or attapulgite zircon silicate, or a porous refractory metal. 壁流式基材还可以由陶瓷纤维复合物材料形成。 Wall flow substrates can also be formed of ceramic fiber composite materials. 优选壁流式基材由堇青石和金钢砂形成。 Preferred wall flow substrates are formed from cordierite and corundum. 这种材料能够有耐受环境,特别是处理废气流时遇到的高温。 This material is capable of withstand the environment, particularly high temperatures encountered in the process exhaust stream.

[0079]本发明的废气处理系统可以进一步包含选择性催化还原(SCR)组分。 [0079] The exhaust gas treatment system of the present invention may further comprise a selective catalytic reduction (SCR) component. SCR组分可以位于DOC和/或烟灰过滤器的上游或者下游。 SCR components may be located upstream or downstream of DOC and / or soot filter. 优选SCR组分位于烟灰过滤器组分的下游。 SCR component is preferably located downstream of the soot filter components. 用于排放物处理系统中的适宜的SCR催化剂组分能够在600°C以下的温度下有效地催化NO x组分的还原反应,以使甚至在通常与较低废气温度相关的低负荷条件下对高水平的NOx进行处理。 Suitable reduction SCR catalyst component emissions treatment system can effectively catalyze the NO x components at a temperature of 600 ° C or less, so that under low load conditions normally associated with a lower exhaust gas temperature even in high levels of NOx to be processed. 优选根据加入系统中的还原剂的量,催化制品能够将至少50%的NO x组分转化为N2。 The amount of reducing agent is preferably added to the system, the catalytic article can be at least 50% of the NO x components is converted to N2. 该复合物的另一个理想属性是其具有催化O2与任意过量的NH 3反应成为犯和出0的能力,以使NH3 不会排放到大气中。 Another desirable property of the composite is that it has a catalytic reaction NH 3 O2 with any excess committed and the ability to become 0 so that NH3 is not emitted into the atmosphere. 可以用于排放物处理系统的SCR催化剂复合物还应当具有对650 °C以上温度的耐热性。 SCR catalyst composite can be used in the emission treatment system should also have thermal resistance to temperatures above 650 ° C. 这种高温在上游催化烟灰过滤器再生过程中可能遇到。 Such high temperatures may be encountered upstream of the catalytic soot filter regeneration process.

[0080]适宜的SCR催化剂复合物描述于例如第4,961,917号美国专利('917专利)和第5, 516,497号美国专利中,二者作为整体通过引用并入本文。 [0080] Suitable SCR catalyst composite is described, for example, U.S. Patent No. 4,961,917 ( '917 patent) and 5, U.S. Patent No., both as a whole by reference No. 516,497 is incorporated herein. '917专利中公开的复合物包含铁和铜促进剂中的一种或者两种,其存在于沸石中的量是促进剂加沸石总重量的大约0.1至30重量百分比,优选大约1至5重量百分比。 '917 patent discloses a complex comprising iron and one or two copper accelerators, which are present in the zeolite in an amount from about 0.1 to 30 weight percent of the total weight of promoter plus zeolite, preferably from about 1 to 5 wt. percentage. 除了催化NO x和NH3还原成为犯之外,所公开的复合物还可以促进过量的NH3与O2发生氧化反应,特别是对于促进剂浓度较高的那些复合物。 In addition to the catalytic reduction of NO x and NH3 become committed, the disclosed composite can also facilitate excess NH3 with O2 oxidation reactions, in particular for the promotion of high concentrations of those compounds. 该系统进一步包含NOx储存和释放(NSR)催化制品。 The system further comprises a NOx storage and release (NSR) catalytic article. 在某些实施方案中,系统中包含SCR或者NSR催化制品中的一种或者另一种。 In certain embodiments, the system comprises a NSR catalyst or SCR article in one or the other.

[0081]在一个实施方案中,本发明涉及包含一种或者多种附加成分的排放物处理系统, 以处理柴油废气排放物。 [0081] In one embodiment, the present invention relates to compositions comprising one or more additional emission treatment system components, to treat diesel exhaust emissions. 通过引用图4可以更容易地领会一种示例性排放物处理系统,所述图4根据本发明的该实施方案描述排放物处理系统32的图示。 By reference to FIG. 4 may be more readily appreciated an exemplary emission treatment system, the emission treatment system 32 illustrated in the FIG. 4 embodiment is described according to this embodiment of the present invention. 参考图4,含有气体污染物(例如未燃烃、一氧化碳和NO x)和颗粒物质的废气流通过线36从发动机34传送至涂有本发明的新型洗涂层复合物的柴油氧化催化剂(D0C)38。 Referring to Figure 4, containing gaseous pollutants (e.g., unburned hydrocarbons, carbon monoxide, and NO x) and particulate matter in the exhaust gas stream via line 36 from the engine 34 transmitted to the diesel oxidation catalyst coated with washcoat new complex of the present invention (d0c ) 38. 在DOC 38中,未燃烧的气态和非挥发性烃(即S0F)以及一氧化碳大部分燃烧形成二氧化碳和水。 In the DOC 38, unburned gaseous and non-volatile hydrocarbons (i.e. S0F are) and most of the combustion of carbon monoxide to form carbon dioxide and water. 此外,NOx组分的一部分NO可以在DOC 中氧化成为N02。 Further, a portion of the NOx component may oxidized to NO N02 in the DOC. 接着废气流通过线40传送至捕获废气流内部存在的颗粒物质的催化烟灰过滤器(CSF)42。 Subsequently the exhaust gas stream through a catalyzed soot filter to capture the internal transmission line 40 present in the exhaust stream of particulate matter (CSF) 42. 任选地,对CSF 42进行催化,以使其被动再生。 Optionally, a catalytic CSF 42, so as to passive regeneration. 通过CSF 42去除颗粒物质后,废气流通过线44传送至下游选择性催化还原(SCR)元件16,以对NOx进行处理和/或转化。 After removal of particulate matter through the CSF 42, the exhaust gas flow downstream of the selective catalytic reduction (SCR) element through the transmission lines 44 to 16, for processing and / or conversion of NOx. DOC 38可以处于紧密耦合位置。 DOC 38 may be in a tightly coupled position.

[0082]本发明的一个或者多个实施方案涉及处理包含C0、HC和NOx的柴油废气流的方法。 [0082] One or more embodiments of the present invention relates to a process comprising C0, HC and NOx methods diesel exhaust stream. 首先使废气流通过包含一个洗涂层(含有铂和钯组分中的一种或者多种)和一种耐火金属氧化物负载体的DOC第一洗涂层区。 First, the exhaust gas stream through a washcoat comprising the DOC (platinum and palladium containing one or more component) and one refractory metal oxide support of the first washcoat zone. 接着使废气通过包含第二洗涂层(含有铂和钯组分中的一种或者多种)和第二耐火金属氧化物负载体的第二洗涂层区。 Then the exhaust gas through a second washcoat layer comprising a second washcoat zone (platinum and palladium containing one or more component) and a second refractory metal oxide support body. 金属的分布使得第一洗涂层中含有钯总量的至少大约50%并且第二洗涂层中含有铂总量的至少大约50%。 Distribution of the metal is such that the total amount of the first washcoat layer contains at least about 50% palladium and a second washcoat layer containing a platinum amount of at least about 50%.

[0083]在其他实施方案中,将与第二洗涂层接触后的柴油废气流引入位于柴油氧化催化剂下游的催化烟灰过滤器(CSF)。 [0083] diesel exhaust stream into the other embodiments, the second washcoat layer positioned in contact with catalyzed diesel soot filter downstream of the oxidation catalyst (CSF). 在进一步的实施方案中,将与催化烟灰过滤器(CSF)接触后的柴油废气流引入位于催化烟灰过滤器(CSF)下游的选择性催化还原(SCR)组分。 Diesel exhaust stream is introduced after a further embodiment, the contact with the catalytic soot filter (CSF) located at the catalyzed soot filter (CSF) downstream of the selective catalytic reduction (SCR) component.

[0084] 本文中公开的DOC催化剂复合物可以用作稳定的紧耦合催化剂。 [0084] DOC disclosed herein may be used as a stable catalyst composite tight coupling catalyst. 紧耦合催化剂与发动机紧密放置,以使其能够尽快达到反应温度。 Tightly coupled catalyst is placed close to the engine, in order to enable it to reach reaction temperatures as soon as possible. 在特定的实施方案中,紧耦合催化剂放置于发动机3英尺以内,更具体地1英尺以内,并且更具体地距离发动机不到6英寸。 In a particular embodiment, the catalyst is placed in tight coupling within 3 feet of the engine, and more particularly less than 1 foot, and more particularly less than 6 inches from the engine. 紧耦合催化剂通常直接附着于废气歧管上。 Tight coupling catalyst is generally attached directly to the exhaust manifold. 由于其与发动机非常接近,优选紧耦合催化剂在高温下是稳定的。 Because of its close proximity to the engine, close-coupled catalysts are preferably stable at high temperatures.

[0085] 根据本发明的特定实施方案将在下面实施例中描述。 [0085] According to a particular embodiment of the present invention will be described in the following examples. 实施例仅是说明性的,并不意味着以任何方式限制本文公开的剩余部分。 Example embodiments are merely illustrative and are not meant to limit in any way the remainder of the disclosure herein. 尽管本说明书强调使柴油发动机的污染物氧化,本文中描述的氧化催化剂可以用于其他催化反应,例如汽油发动机中CO和烃的氧化。 While this specification emphasizes the diesel oxidation contaminants, oxidation catalysts described herein may be used in other catalytic reactions, such as oxidation of CO and hydrocarbons in the gasoline engine of.

[0086] 在描述本发明的几个示例性实施方案之前,应当理解的是,下面描述中阐述的构造或者过程步骤的细节并不限制本发明。 [0086] Before describing several exemplary embodiments of the present invention, it should be understood that the details of construction or process steps set forth in the following description do not limit the present invention. 本发明可以是其他实施方案并且能够以多种方式实施。 The present invention is capable of other embodiments and of being practiced in various ways. 下面提供了分层催化剂的优选设计,其中包括如所列举单独使用或者无限制组合使用的复合物,其用途包括本发明其他方面的系统和方法。 The following provides a preferred layered catalyst design, including as recited used alone or in combination with unrestricted composite, which comprises the use of the present invention is a system and method for others. 实施例 Example

[0087] 参考样品A [0087] A reference sample

[0088]通过将含有Pt和Pd的水性浆料涂于"直径4.66"乘以长度6""的堇青石蜂巢型单片基材(400cpsi,壁厚4mil)上,利用OSC上的Pd和氧化错上的Pt的均勾混合物制备洗涂层的Pt/Pd催化剂复合物。 Cordierite honeycomb monolithic substrate (400 cpsi, wall thickness of 4mil) [0088] by an aqueous slurry containing Pt and Pd is applied "diameter 4.66" 6 times the length of "", the use of Pd oxide on OSC each hook on the wrong mixture of Pt washcoat Pt / Pd catalyst composite prepared. 贵金属的总承载量是110g/ft3,Pt/Pd比率是1:2。 The total carrying amount of noble metal is 110g / ft3, Pt / Pd ratio is 1: 2. 含有Pt和Pd的水性浆料制备如下: Preparing an aqueous slurry containing Pt and Pd are as follows:

[0089] 利用标准的初湿含浸技术用水溶性Pd盐浸渍含有20 %二氧化铺、6 %氧化钕、6 % 氧化镧和68 %氧化锆并且具有大约90m2/g的BET表面积的OSC材料。 [0089] using standard incipient wetness techniques plated containing 20% ​​silica impregnated with a water-soluble Pd salt, neodymium oxide 6%, 6% and 68% lanthanum oxide and zirconium oxide having a BET surface area of ​​the OSC material of about 90m2 / g to. 分别地,利用标准的初湿含浸技术用水溶性Pd盐浸渍具有大约150m 2/g的BET表面积、大约0.4cc/g的孔体积和大约50A的平均孔径的高比表面积γ_氧化铝。 Separately, using a standard incipient wetness technique has about 150m 2 / g BET surface area impregnated with a water-soluble Pd salt, high pore volume of about 0.4cc / g and an average pore size of about 50A γ_ specific surface area alumina. 用无机酸进一步浸渍该粉末。 The powder was further impregnated with an inorganic acid. 将得到的Pd/ OSC和Pt/氧化铝浸渍粉末置于含有乙酸锆的DI水中(以ZrO2重量计算的总浆料固体是5%),并通过加入有机酸使得到的水性浆料的pH值降至3.7。 The resulting Pd / OSC and Pt / alumina powder was placed in DI water containing impregnating zirconium acetate (total weight ZrO2 slurry solids was 5%), and the pH of the aqueous slurry obtained by adding an organic acid to 3.7. 利用本领域已知的方法通过研磨将90%的颗粒大小减少至小于IOum后,利用也是本领域已知的沉积方法将浆料涂于堇青石基材上。 Methods known in the art reduction by grinding to a particle size of 90% less than IOum after deposition using known methods in the art will also slurry was applied on a cordierite substrate. 使经涂层的单片干燥,并接着于550Γ煅烧lh。 The coated monolithic so dried and then calcined at 550Γ lh. 煅烧后洗涂层的总承载量是大约1.6g/in 3,其中OSC材料含有大约1.0 g/in3,氧化铝含有0.5g/in3。 The total loading of washcoat after calcination is about 1.6g / in 3, wherein the OSC material containing about 1.0 g / in3, alumina contains 0.5g / in3. 用类似方法将第二层涂于第一层上,并使两次涂层的单片干燥,于550°C再次煅烧lh。 In a similar manner a second layer coated on the first layer, coating and drying two monolithic, lh calcined at 550 ° C again. 煅烧后第二层洗涂层的总承载量是大约1.6g/in 3,其中OSC材料含有大约1.0 g/in3,氧化铝含有0.5g/in3。 The total amount of the carrier after calcination second washcoat layer is about 1.6g / in 3, wherein the OSC material containing about 1.0 g / in3, alumina contains 0.5g / in3.

[0090] 参考样品B [0090] Reference Sample B

[0091] 通过将含有Pt和Pd的水性浆料涂于"直径4.66"乘以长度6""的堇青石蜂巢型单片基材(400cpsi,壁厚4mi 1)上,利用OSC上的Pd、氧化错上的Pt和β-沸石的均勾混合物制备洗涂层的Pt/Pd催化剂复合物。 Cordierite honeycomb monolithic substrate (400 cpsi, wall thickness 4mi 1) [0091] by an aqueous slurry containing Pt and Pd is applied "diameter 4.66" 6 times the length of "", the use of Pd on the OSC, the mixture was hook β- zeolite and Pt oxide on the washcoat wrong Pt / Pd catalyst composite prepared. 贵金属的总承载量是150g/ft 3,Pt/Pd比率是1:2。 The total amount of noble metal is carrying 150g / ft 3, Pt / Pd ratio is 1: 2. 含有Pt和Pd 的水性浆料制备如下: Preparing an aqueous slurry containing Pt and Pd are as follows:

[0092] 利用标准的初湿含浸技术用水溶性Pd盐浸渍含有20 %二氧化铺、6 %氧化钕、6 % 氧化镧和68 %氧化锆并且具有大约90m2/g的BET表面积的OSC材料。 [0092] using standard incipient wetness techniques plated containing 20% ​​silica impregnated with a water-soluble Pd salt, neodymium oxide 6%, 6% and 68% lanthanum oxide and zirconium oxide having a BET surface area of ​​the OSC material of about 90m2 / g to. 分别地,利用标准的初湿含浸技术用水溶性Pd盐浸渍具有大约150m 2/g的BET表面积、大约0.4cc/g的孔体积和大约的平均孔径的高比表面积丫-氧化铝。 Separately, using a standard incipient wetness technique has about 150m 2 / g BET surface area impregnated with a water-soluble Pd salt, about 0.4cc / g and a pore volume of high specific surface area of ​​an average pore diameter of about Ah - alumina. 用无机酸进一步浸渍该粉末。 The powder was further impregnated with an inorganic acid. 将得到的Pd/ OSC和Pt/氧化铝浸渍粉末置于含有乙酸锆的DI水中(以ZrO2重量计算的总浆料固体是5%),并通过加入有机酸使得到的水性浆料的pH值降至3.7。 The resulting Pd / OSC and Pt / alumina powder was placed in DI water containing impregnating zirconium acetate (total weight ZrO2 slurry solids was 5%), and the pH of the aqueous slurry obtained by adding an organic acid to 3.7. 利用本领域已知的方法通过研磨将90 %的颗粒大小减少至小于IOum后,加入干燥Η-β沸石。 Methods known in the art reduction by grinding to a particle size of 90% less than IOum added after drying Η-β zeolite. 在进一步通过研磨将90 %的颗粒大小减少至小于9um后,利用也是本领域已知的沉积方法将浆料涂于堇青石基材上。 In a further 90% reduction in the particle size by milling to less than the 9um using deposition methods known in the art slurry is coated on a cordierite substrate. 使经涂层的单片干燥,并接着于550Γ煅烧lh。 The coated monolithic so dried and then calcined at 550Γ lh. 煅烧后洗涂层的总承载量是大约1.6g/in 3,其中OSC材料含有大约0 · 75g/in3,氧化铝含有0 · 5g/in3,Η-β-沸石含有0 · 25g/in3。 The total loading of washcoat after calcination is about 1.6g / in 3, wherein the OSC material comprises from about 0 · 75g / in3, alumina contains 0 · 5g / in3, Η-β- zeolite contains 0 · 25g / in3. 用类似方法将第二层涂于第一层上,并使两次涂层的单片干燥,于550°C再次煅烧lh。 In a similar manner a second layer coated on the first layer, coating and drying two monolithic, lh calcined at 550 ° C again. 煅烧后第二层洗涂层的总承载量是大约1.6g/in 3,其中OSC材料含有大约0.75g/in3,氧化铝含有0.5g/in3,H-沸石含有〇.25g/in 3。 The total amount of the carrier after calcination second washcoat layer is about 1.6g / in 3, wherein the OSC material contained approximately 0.75g / in3, alumina contains 0.5g / in3, H- zeolite contains 〇.25g / in 3.

[0093] 参考样品C [0093] Reference Sample C

[0094]通过将含有Pt的水性浆料涂于"直径4.66"乘以长度6""的堇青石蜂巢型单片基材(400cpsi,壁厚4mil)上,利用二氧化硅-氧化铝上的Pt和β-沸石的均匀混合物制备仅含Pt 的洗涂层催化剂复合物。 Cordierite honeycomb monolithic substrate (400 cpsi, wall thickness of 4mil) [0094] by an aqueous slurry containing Pt is applied "diameter 4.66" 6 times the length of "", the use of silica - alumina on Pt and a homogeneous mixture prepared β- zeolite containing only Pt washcoat catalyst composite. 贵金属的总承载量是ll〇g/ft3。 The total amount of noble metal is carried ll〇g / ft3. 含有Pt的水性浆料制备如下: Preparing an aqueous slurry containing Pt as follows:

[0095]利用标准的初湿含浸技术用水溶性Pt盐浸渍具有大约120m2/g的BET表面积、大约0.7cc/g的孔体积和大于80盖的平均孔径的的高表面积二氧化硅-氧化铝(5%的二氧化硅)。 High surface area silica [0095] using standard incipient wetness techniques have about 120m2 / g BET surface area impregnated with the water-soluble salts of Pt, about 0.7cc / g pore volume and average pore diameter of greater than 80 of the cap - alumina ( 5% silica). 用无机酸进一步浸渍该粉末。 The powder was further impregnated with an inorganic acid. 将得到的Pt/二氧化硅-氧化铝浸渍粉末置于含有Η-β-沸石的DI水中,并通过加入有机酸使得到的水性浆料的pH值降至4。 The resulting Pt / silica - alumina powder was placed in DI water containing immersed Η-β- zeolite, and by adding an organic acid that the pH of the aqueous slurry obtained to 4. 利用本领域已知的方法通过研磨将90%的颗粒大小减少至小于12um后,利用也是本领域已知的沉积方法将浆料涂于堇青石基材上。 Methods known in the art reduction by grinding to a particle size of 90% less than 12um after deposition using known methods in the art will also slurry was applied on a cordierite substrate. 使经涂层的单片干燥,并接着于500Γ煅烧lh。 The coated monolithic so dried and then calcined at 500Γ lh. 煅烧后洗涂层的总承载量是大约lg/in3,其中二氧化硅-氧化铝含有大约0.75g/in 3,Η-β-沸石含有0.25g/in3。 The total loading of washcoat after calcination is about lg / in3, wherein the silica - alumina contains about 0.75g / in 3, Η-β- zeolite containing 0.25g / in3. 用类似方法将第二层涂于第一层上,并使两洗涂层的单片干燥,于500°C再次煅烧lh。 In a similar manner a second layer coated on the first layer, and two washcoat monolithic dried, calcined at 500 ° C again lh. 煅烧后第二层洗涂层的总承载量是大约lg/in 3,其中二氧化硅-氧化铝含有大约0.75g/in3,H-i3-沸石含有0.25g/in 3〇[0096] 分区样品DG The total loading of the second washcoat layer after firing is about lg / in 3, wherein the silica - alumina contains about 0.75g / in3, H-i3- zeolite containing 0.25g / in 3〇 [0096] Samples partition DG

[0097] 对CO和HC NEDC性能进行测定后,将参考样品A、B和C中的每个样品沿长度(即长度中间的点)切成两半,以产生与参考样品AC前半段和后半段相对应的"宽度4.66"乘以长度3.0""的经涂覆单片。 [0097] CO and HC NEDC after performance of the assay, the reference sample A, B and C along the length of each sample (i.e., the middle point of the length) was cut in half to generate the reference sample and the first half of the AC and corresponding to half the "width 4.66" 3.0 times the length of "" the coated monolithic. 接着将这些背对背地结合成特定的组合,产生对比例D、E、F和G,以模拟不同的区段配置。 These back to back and then combined into a particular combination, to produce Comparative Example D, E, F and G, in order to simulate different sector layout. 对比例D包括参考样品C的前半段(仅含Pt)和参考样品A的后半段。 Half of the Comparative Example D comprises a first half (containing only Pt) reference samples C and A in the reference sample. 相反地,对比例E包括参考样品A的前半段和参考样品C的后半段(仅含Pt)。 In contrast, Comparative Example E A first half of the reference sample and the reference includes a second half of the sample C (containing only Pt). 对比例F包括参考样品C的前半段(仅含Pt)和参考样品B的后半段。 Comparative Example F of the front half of the reference sample comprises a C (containing only Pt), and a reference sample B after the half segment. 相反地,对比例G包括参考样品B的前半段(仅含Pt)和参考样品C的后半段(仅含Pt)。 In contrast, Comparative Example G comprising the latter half (containing only Pt), and a reference sample of the first half of the reference C Sample B (containing only Pt). 对新的对比性"分区"样品进行与如上面所描述对参考样品AC类似的CO和HC性能评估。 Comparative new "partitioning" samples as described above and similar to CO and HC performance evaluation of the reference sample AC. 测试结果显示于图5和6以及表1中。 The test results are shown in FIGS. 5 and 6 and Table 1.

[0098] 样品测试 [0098] Test samples

[0099]用下列方法对实施例1-3中制备的洗涂层催化剂复合物进行测试:首先将经涂覆单片安装于测试柴油发动机的废气流中,并接着使其发生高温后喷射(post-injection, PI)老化。 [0099] carried out by the following methods washcoat catalyst composite prepared in Example 1-3 tests performed: First a test is attached to the exhaust stream of a diesel engine monolithic coated, and then allowed to high temperatures occurs after injection ( post-injection, PI) aging. 这通过使催化剂前端面的温度保持在400°C并接着周期性地将燃料喷射到催化剂前面的废气流中来完成。 It is maintained at 400 ° C and then periodically injecting fuel into the exhaust gas stream in front of the catalyst is accomplished by the front end surface of the catalyst temperature. 所喷射的燃料进入催化剂并燃烧,因而使催化剂后端面测得的温度增加。 The catalyst was injected into the fuel combustion, the temperature of the end face thus measured after the catalyst increases. 通过控制喷射入废气流中的燃料量来控制催化剂后端面的温度。 After the catalyst is controlled by controlling the temperature of the end face of the amount of fuel injected into the exhaust stream. 利用这种方法,催化剂后端面的温度以15分钟的时间间隔在400°C和700°C之间循环25小时(总共50个循环)。 With this method, the temperature of the end face of the catalyst after 15 minute intervals between 400 ° C and 700 ° C cycle 25 hours (total 50 cycles). [0100]老化后,利用欧洲轻型车辆认证新排放驾驶循环(NEDC)对经涂覆单片对于测试发动机CO和HC的性能进行评估。 [0100] After aging, the new authentication emissions driving cycle (the NEDC) on a vehicle using light European coated monolithic assess engine performance tests for CO and HC. 将单片单独安装于3L BMW M57发动机(欧4标准)的废气流中, 所述发动机在NEDC循环中向外排放1.6g/km的CO和0.4g/km的HC。 The exhaust gas stream is mounted on a single piece separate 3L BMW M57 engine (Euro 4), said engine exhaust CO and 0.4g / km of HC 1.6g / km outwardly NEDC cycle. 随着根据NEDC循环的说明"启动"发动机,在经涂覆单片的前面和后面监测CO和HC浓度,以计算催化剂对CO和HC的转化。 With the "start" engine conversion, the monolithic coated front and back by monitoring the concentration of CO and HC to CO and HC for the calculation of the catalyst according to the instructions of the NEDC cycle. 测试后,如前面所描述将实施例AC中制备的单片切成两半,以制备实施例DG。 After the test, as previously prepared in Example AC monolithic embodiments will be described cut in half to prepare Example DG. 实施例AG中制备的经涂覆单片的测试结果显示于图5和6以及表1中。 The test results of the coated monolithic Preparation AG and the embodiment shown in FIG. 6 and Table 1 5.

[0101] 如图5和6中所显示,分区样品DG的柴油发动机台架测试显示,于700°C进行25小时的后喷射老化后,前区涂有Pt/Pd催化剂洗涂层制剂并且后区涂有仅含Pt的洗涂层制剂的单片与复合物和贵金属的分布相反的分区涂覆的单片相比,对CO和HC的氧化显著较好。 [0101] FIG. 5 and 6 show, the partition sample DG diesel engine bench tests show, for 25 hours after the injection at 700 ° C After aging, the front region coated with Pt / Pd catalyst and washcoat formulation after monolithic coated opposite partition distribution area is coated with a formulation containing only Pt washcoat of a precious metal and a single piece with the complex as compared to the oxidation of CO and HC significantly better. 事实上,利用这种新型的洗涂层方案(对比性样品D和F,与参考样品C相比)获得了与本领域最先进的仅含Pt的DOC催化剂相同的结果。 In fact, by using this new scheme washcoat (Comparative Samples D and F., As compared to the reference sample C) obtained with the same Pt ​​containing only the most advanced art DOC catalyst according to the present results. 这些结果是出乎意料的,因为通常认为Pt位于前区时更有效,在前区其免受通常与后区定位相关的高温放热。 These results are surprising, because usually considered to be more effective when Pt is located in the front region, which region is typically positioned against the front high-temperature heat associated with the rear region. 由于利用这种新型的分区方案显示Pt/Pd催化剂可以获得与仅含Pt的催化剂相同的结果,因此存在降低DOC总体成本的重大机会。 Due to the use of this new partition scheme is displayed Pt / Pd catalyst can be obtained with a catalyst containing only Pt same results, so there is significant opportunity to reduce the overall cost of the DOC. 此外,利用这种分区方案特别有益于消除与先进燃烧发动机相关的高水平CO和HC(特别是甲烷)。 In addition, with this partitioning scheme is particularly beneficial to eliminate the combustion engine associated with advanced high level of CO and HC (in particular methane). 结果总结于下面的表中。 The results are summarized in the table below.

Figure CN102387856BD00181

L0103」尽管已经在标准(欧4)柴油发动机上显示所描述的多个实施方案,本发明可以在标准柴油和先进燃烧柴油应用中使用。 L0103 "Although various embodiments have been shown in the described standard (Euro 4) diesel engine, the present invention can be used in a standard diesel combustion and advanced diesel applications.

[0104] 本说明书中所涉及的"一个实施方案"、"特定实施方案"、"一个或者多个实施方案"是指发明中包括与实施方案同时描述的具体性质、结构、材料或者特性。 [0104] in this specification to "one embodiment," "certain embodiment," "one or more embodiments" means that the specific nature of the invention include, structure, material, or characteristic described embodiments simultaneously. 此外,本说明书中多处出现的词组例如"在一个或者多个实施方案中"、"在特定的实施方案中"、"在一个实施方案中"并不是指本发明相同的实施方案。 In addition, phrases in various places in the present specification, such as "in one or more embodiments," "in certain embodiments", "in one embodiment" does not refer to the same embodiment of the present invention. 此外,具体性质、结构、材料或者特性可以以任何适宜的方式结合于一个或者多个实施方案中。 Furthermore, the particular nature of the structures, materials, or characteristics may be combined in one or more embodiments in any suitable manner.

[0105] 尽管本文中已经根据特定的实施方案对本发明进行了描述,将可以理解的是,这些实施方案仅仅是为了说明本发明的原理和应用。 [0105] Although the invention herein has been described in terms of particular embodiments, it will be understood that these embodiments are merely illustrative of the principles and applications of the present invention. 对于本领域技术人'员显而易见的是,可以在不偏离本发明的精神和范围的情况下对本发明的方法和设备进行多种修饰和变化。 For the person skilled in the art 'members will be apparent that various modifications and variations can be made to the method and apparatus of the invention without departing from the spirit and scope of the invention. 因此,这意味着本发明包括在所附权利要求和其等价物范围内的修饰和变化。 Thus, this means that the present invention include modifications and variations in the appended claims and their equivalents range.

Claims (14)

1. 一种用于消除发动机废气排放物的氧化催化剂复合物,包含:具有一定长度、入口端和出口端的载体基材,所述载体基材上的柴油氧化催化剂催化材料,包括第一洗涂层区和第二洗涂层区的柴油氧化催化剂催化材料;所述第一洗涂层区包含第一洗涂层和第一耐火金属氧化物负载体,所述第一洗涂层含有铂和钯组分的混合物,所述第一洗涂层区与所述载体基材的所述入口端相邻;以及所述第二洗涂层区包含第二洗涂层和第二耐火金属氧化物负载体,所述第二洗涂层含有铂组分,所述第二洗涂层区与所述载体基材的所述出口端相邻,其中钯组分总量的至少50%位于所述第一洗涂层区中,铂组分总量的至少50% 位于所述第二洗涂层区中;并且其中第二洗涂层基本不含钯。 An engine exhaust emissions for eliminating oxidation catalyst composite, comprising: having a length, the inlet and outlet ends of the carrier substrate, the carrier diesel oxidation catalyst catalytic material on a substrate, comprising a first wash coating diesel oxidation catalyst zone and the second catalytic material washcoat layer region; the first washcoat layer comprising a first washcoat zone and the first refractory metal oxide support, the first washcoat comprising platinum and palladium component, a first wash zone and the inlet end of the coating adjacent carrier substrate; and the second washcoat zone comprises a second washcoat layer and a second refractory metal oxide the load body, the second washcoat layer containing a platinum component, the outlet end of the second washcoat zone adjacent the carrier substrate, wherein at least 50% of the palladium component located a first washcoat zone, at least 50% of the total platinum component located in the second washcoat zone; and wherein the second washcoat layer substantially free of palladium.
2. 权利要求1的氧化催化剂复合物,其中所述第一洗涂层区延伸至所述基材的全长,并且所述第二洗涂层区与所述第一洗涂层区的至少一部分重叠。 At least an oxidation catalyst composite of claim 1, wherein said first wash extends to the entire length of the substrate coating region and the second region and the first washcoat zone washcoat partially overlap.
3. 权利要求1的氧化催化剂复合物,其中所述第一洗涂层区从所述入口端延伸至所述基材长度的5%至95%,并且所述第二洗涂层区从所述出口端延伸至所述基材长度的5%至95%〇 Oxidation catalyst composite of claim 1, wherein the first washcoat zone extending from the inlet end to the 5 to 95% of the length of the substrate, and the second washcoat layer from the region said outlet end extending to the length of the substrate 5-95% billion
4. 权利要求3的氧化催化剂复合物,其中所述第一洗涂层区和所述第二洗涂层区相互重叠。 Oxidation catalyst composite according to claim 3, wherein the first washcoat and the second washcoat zone overlap region.
5. 权利要求1的氧化催化剂复合物,其中所述铂和所述钯以铂总量与钯总量的比率从1:10至4:1存在。 Oxidation catalyst composite of claim 1, wherein said platinum and palladium in a ratio of said total amount of platinum and palladium from 1:10 to 4: 1 is present.
6. 权利要求1的氧化催化剂复合物,其中所述催化材料有效地使先进燃烧柴油发动机排放的、包括甲烷组分的HC和CO氧化,所述第一洗涂层区活化以用于在与所述先进燃烧柴油发动机运行相关的高排放和低温条件下使CO和HC氧化,所述先进燃烧柴油发动机通过点火前使发动机气缸内部燃烧火焰的温度降低和增加燃料供给的一致性和混合度来运行。 Oxidation catalyst composite of claim 1, wherein the catalytic material effective to advanced combustion diesel engine emissions, including methane HC and CO oxidation component, the first washcoat zone and for activated to the advanced oxidation combustion of CO and HC emissions under high and low temperature conditions related to the operation of the diesel engine, the diesel engine by combustion advanced before ignition internal combustion engine cylinder to reduce temperature of the flame and increasing the fuel supply to the consistency and degree of mixing run.
7. 权利要求1的氧化催化剂复合物,其中所述第一耐火金属氧化物负载体和所述第二耐火金属氧化物负载体之一或者二者包含氧化铝、二氧化硅、氧化锆、二氧化钛和其组合中的一种或者多种。 Oxidation catalyst composite of claim 1, wherein one of said first refractory metal oxide support and said second refractory metal oxide support, or both comprises alumina, silica, zirconia, titania and one or more combinations thereof.
8. 权利要求1的氧化催化剂复合物,其中所述第一洗涂层和所述第二洗涂层之一或者二者进一步包含沸石、碱土氧化物、稀土氧化物和贱金属氧化物中的一种或者多种。 Oxidation catalyst composite of claim 1, wherein said first and said second coating layer washed one or both washcoat layer further comprises zeolite, alkaline earth oxides, rare earth oxides and base metal oxide one or more.
9. 权利要求1的氧化催化剂复合物,进一步包含基本不含贵族金属组分的底涂层,所述底涂层在所述第一洗涂层区和所述第二洗涂层区之一或者二者的下面而涂覆于所述载体基材上。 9. The composite oxide catalyst as claimed in claim 1, further comprising an undercoat layer is substantially free of noble metal component, the undercoat washcoat layer region in said first and said second coating one wash zone or both below and coated on the carrier substrate.
10. 权利要求1的氧化催化剂复合物,其中所述第一耐火金属氧化物负载体包含二氧化铈和含有沸石的分子筛,所述沸石选自β-沸石、ZSM-5或者沸石-Y。 10. The oxidation catalyst composite of claim 1, wherein said first refractory metal oxide support comprises ceria and a zeolite-containing molecular sieve, the zeolite is selected from β- zeolite, ZSM-5 zeolite or -Y.
11. 权利要求1的氧化催化剂复合物,其中所述催化剂复合物具有30g/f t3至350g/f t3范围的钼和钯总承载量。 11. The oxidation catalyst composite of claim 1, wherein the catalyst composite has a 30g / f t3 to 350g / molybdenum and palladium total loading range of f t3.
12. -种用于处理柴油废气流的方法,包括使传统柴油废气流或者先进燃烧柴油废气流通过催化烟灰过滤器,所述废气流首先通过权利要求1-11中任一项的氧化催化剂复合物。 12. - a kind of a diesel exhaust gas stream, including diesel exhaust stream traditional or advanced diesel exhaust stream through a catalytic combustion soot filter, the exhaust gas stream through the first oxidation catalyst composite as claimed in claim any one 1-11 thereof.
13. 权利要求12的方法,进一步包括将传统柴油废气流或者先进燃烧柴油废气流引入位于所述催化烟灰过滤器下游的选择性催化还原催化制品。 13. The method of claim 12, further comprising a conventional or advanced diesel exhaust stream selective catalytic combustion of diesel exhaust stream into the catalytic soot filter is located downstream of the reduction catalytic article.
14. 权利要求12的方法,包括在与先进燃烧柴油发动机运行相关的高排放和低温条件下使CO和HC氧化。 14. The method of claim 12, comprising the oxidation of CO and HC emissions at high and low temperatures and advanced diesel engine operation associated with the burning.
CN201080014918.1A 2009-04-08 2010-04-07 The catalyst for diesel applications partition CN102387856B (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US16757509P true 2009-04-08 2009-04-08
US61/167,575 2009-04-08
US12/755,032 2010-04-06
US12/755,032 US8637426B2 (en) 2009-04-08 2010-04-06 Zoned catalysts for diesel applications
PCT/US2010/030226 WO2010118125A2 (en) 2009-04-08 2010-04-07 Zoned catalysts for diesel applications

Publications (2)

Publication Number Publication Date
CN102387856A CN102387856A (en) 2012-03-21
CN102387856B true CN102387856B (en) 2016-07-20

Family

ID=42933232

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201080014918.1A CN102387856B (en) 2009-04-08 2010-04-07 The catalyst for diesel applications partition

Country Status (7)

Country Link
US (1) US8637426B2 (en)
EP (1) EP2416877A4 (en)
JP (1) JP5730282B2 (en)
KR (3) KR20190073617A (en)
CN (1) CN102387856B (en)
BR (1) BRPI1015175B1 (en)
WO (1) WO2010118125A2 (en)

Families Citing this family (63)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2112339A1 (en) * 2008-04-24 2009-10-28 Umicore AG &amp; Co. KG Method and device for cleaning exhaust gases of a combustion motor
US8246923B2 (en) 2009-05-18 2012-08-21 Umicore Ag & Co. Kg High Pd content diesel oxidation catalysts with improved hydrothermal durability
US8557203B2 (en) 2009-11-03 2013-10-15 Umicore Ag & Co. Kg Architectural diesel oxidation catalyst for enhanced NO2 generator
US8833064B2 (en) * 2009-11-06 2014-09-16 Basf Corporation Small engine layered catalyst article and method of making
JP5683598B2 (en) 2009-11-12 2015-03-11 ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフトUmicore AG & Co.KG Improved diesel oxidation catalyst
US8734743B2 (en) * 2010-06-10 2014-05-27 Basf Se NOx storage catalyst with improved hydrocarbon conversion activity
US8784759B2 (en) * 2010-06-10 2014-07-22 Basf Se NOx storage catalyst with reduced Rh loading
CN103080047A (en) * 2010-08-31 2013-05-01 康宁股份有限公司 Cellular ceramic articles with coated channels and methods for making the same
US8557204B2 (en) * 2010-11-22 2013-10-15 Umicore Ag & Co. Kg Three-way catalyst having an upstream single-layer catalyst
US8668877B2 (en) 2010-11-24 2014-03-11 Basf Corporation Diesel oxidation catalyst articles and methods of making and using
WO2012079598A1 (en) * 2010-12-14 2012-06-21 Umicore Ag & Co. Kg Architectural diesel oxidation catalyst for enhanced no2 generator
GB201021649D0 (en) * 2010-12-21 2011-02-02 Johnson Matthey Plc NOx Absorber catalyst
GB201021887D0 (en) * 2010-12-21 2011-02-02 Johnson Matthey Plc Oxidation catalyst for a lean burn internal combustion engine
US8591820B2 (en) 2011-03-11 2013-11-26 Corning Incorporated Honeycomb filters for reducing NOx and particulate matter in diesel engine exhaust
JP5938819B2 (en) 2011-10-06 2016-06-22 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Public Limited Company Oxidation catalyst for exhaust gas treatment
WO2013052048A1 (en) * 2011-10-06 2013-04-11 Mack Trucks, Inc. Diesel oxidation catalyst and method of treating engine exhaust gas
GB201200784D0 (en) * 2011-12-12 2012-02-29 Johnson Matthey Plc Exhaust system for a lean-burn internal combustion engine including SCR catalyst
GB2497597A (en) * 2011-12-12 2013-06-19 Johnson Matthey Plc A Catalysed Substrate Monolith with Two Wash-Coats
CN104039425B (en) * 2011-12-22 2016-08-24 庄信万丰股份有限公司 Improved NO <sub> x </ sub> Trap
DE102012005508A1 (en) * 2012-03-17 2013-09-19 Daimler Ag Catalyst component of a motor vehicle emission control system and use of a catalyst component
GB201207313D0 (en) 2012-04-24 2012-06-13 Johnson Matthey Plc Filter substrate comprising three-way catalyst
US8568674B1 (en) 2012-08-10 2013-10-29 Basf Corporation Diesel oxidation catalyst composites
JP2014091119A (en) * 2012-11-07 2014-05-19 Nippon Shokubai Co Ltd Catalyst for combustion of methane and production method of the same
GB201220912D0 (en) 2012-11-21 2013-01-02 Johnson Matthey Plc Oxidation catalyst for treating the exhaust gas of a compression ignition engine
DE112013005743T5 (en) * 2012-11-30 2015-09-10 Johnson Matthey Public Limited Company Ammonia oxidation catalyst
KR101459848B1 (en) * 2012-12-13 2014-11-07 현대자동차주식회사 Diesel oxidation catalyst
KR101427933B1 (en) 2012-12-28 2014-08-11 현대자동차 주식회사 Catalytic converter of internal combustion engine and apparatus of purifying exhaust gas provided with the same
US9266092B2 (en) * 2013-01-24 2016-02-23 Basf Corporation Automotive catalyst composites having a two-metal layer
EP2772302A1 (en) 2013-02-27 2014-09-03 Umicore AG & Co. KG Hexagonal oxidation catalyst
US9333490B2 (en) 2013-03-14 2016-05-10 Basf Corporation Zoned catalyst for diesel applications
GB2512648B (en) * 2013-04-05 2018-06-20 Johnson Matthey Plc Filter substrate comprising three-way catalyst
GB2513364B (en) * 2013-04-24 2019-06-19 Johnson Matthey Plc Positive ignition engine and exhaust system comprising catalysed zone-coated filter substrate
GB2514177A (en) * 2013-05-17 2014-11-19 Johnson Matthey Plc Oxidation catalyst for a compression ignition engine
DE102013210270A1 (en) * 2013-06-03 2014-12-04 Umicore Ag & Co. Kg three-way
BR112016001924A2 (en) * 2013-07-30 2017-08-01 Johnson Matthey Plc catalyst article, system and method for treating exhaust gas
GB201315892D0 (en) * 2013-07-31 2013-10-23 Johnson Matthey Plc Zoned diesel oxidation catalyst
US9808794B2 (en) * 2013-09-23 2017-11-07 Corning Incorporated Honeycomb ceramic substrates, honeycomb extrusion dies, and methods of making honeycomb ceramic substrates
WO2015059904A1 (en) * 2013-10-23 2015-04-30 マツダ株式会社 Exhaust gas purifying catalyst device and method for purifying exhaust gas
US9732648B2 (en) 2013-10-23 2017-08-15 Mazda Motor Corporation Catalyst device for exhaust gas purification and method for exhaust gas purification
JP6102766B2 (en) * 2013-10-23 2017-03-29 マツダ株式会社 Exhaust gas purification catalyst device and exhaust gas purification method
JP2015137605A (en) * 2014-01-23 2015-07-30 マツダ株式会社 Exhaust emission control catalyst device
JP6171947B2 (en) * 2014-01-23 2017-08-02 マツダ株式会社 Exhaust gas purification catalyst device and exhaust gas purification method
US9662636B2 (en) * 2014-04-17 2017-05-30 Basf Corporation Zoned catalyst composites
US9757718B2 (en) * 2014-05-09 2017-09-12 Johnson Matthey Public Limited Company Ammonia slip catalyst having platinum impregnated on high porosity substrates
US20160136617A1 (en) * 2014-11-17 2016-05-19 Clean Diesel Technologies, Inc. Synergized PGM Catalyst with Low PGM Loading and High Sulfur Resistance for Diesel Oxidation Application
US9764286B2 (en) * 2014-12-03 2017-09-19 Ford Global Technologies, Llc Zoned catalyst system for reducing N2O emissions
DE102014226659A1 (en) * 2014-12-19 2016-06-23 Robert Bosch Gmbh A method of operating a methane oxidation catalyst and exhaust aftertreatment system
US9482131B2 (en) 2015-01-08 2016-11-01 Tenneco Automotive Operating Company Inc. Exhaust system with zone coated catalyst
GB2535466A (en) * 2015-02-16 2016-08-24 Johnson Matthey Plc Catalyst with stable nitric oxide (NO) oxidation performance
JP6501115B2 (en) * 2015-05-15 2019-04-17 株式会社 Acr Dual fuel oxidation catalyst, dual fuel SCR exhaust gas treatment mechanism, dual fuel diesel internal combustion engine, and control method therefor
JP2015180498A (en) * 2015-05-19 2015-10-15 ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフトUmicore AG & Co.KG Architectural diesel oxidation catalyst for enhanced no2 generator
MX2017016111A (en) * 2015-06-12 2018-02-21 Basf Corp Exhaust gas treatment system.
US9937489B2 (en) * 2015-06-18 2018-04-10 Johnson Matthey Public Limited Company Exhaust system without a DOC having an ASC acting as a DOC in a system with an SCR catalyst before the ASC
KR20180034397A (en) * 2015-06-18 2018-04-04 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Divisional exhaust system
GB201521123D0 (en) * 2015-11-30 2016-01-13 Johnson Matthey Plc Diesel oxidation catalyst having a capture region for exhaust gas impurities
US20170189892A1 (en) * 2015-12-31 2017-07-06 SDCmaterials, Inc. Layered catalysts for gasoline engine exhaust
US10022671B2 (en) 2016-03-24 2018-07-17 Cataler Corporation Exhaust gas purification device
JP6372513B2 (en) * 2016-04-13 2018-08-15 トヨタ自動車株式会社 Catalytic converter
DE102016207484A1 (en) 2016-05-02 2017-11-02 Umicore Ag & Co. Kg Diesel oxidation catalyst
CN109310991A (en) 2016-07-19 2019-02-05 优美科股份公司及两合公司 Diesel oxidation converter
GB2552546A (en) * 2016-07-29 2018-01-31 Johnson Matthey Plc Oxidation catalyst for a compression ignition engine and a method of preparation therefor
EP3357558B1 (en) 2017-02-03 2019-06-26 Umicore Ag & Co. Kg Catalyst for cleaning diesel engine exhaust gases
CN109201052A (en) * 2018-09-30 2019-01-15 中自环保科技股份有限公司 A kind of diesel soot particle oxidation catalyst and preparation method thereof

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4335023A (en) * 1980-01-24 1982-06-15 Engelhard Corporation Monolithic catalyst member and support therefor
US4961917A (en) * 1989-04-20 1990-10-09 Engelhard Corporation Method for reduction of nitrogen oxides with ammonia using promoted zeolite catalysts
US5024981A (en) * 1989-04-20 1991-06-18 Engelhard Corporation Staged metal-promoted zeolite catalysts and method for catalytic reduction of nitrogen oxides using the same
US5804155A (en) * 1992-11-19 1998-09-08 Engelhard Corporation Basic zeolites as hydrocarbon traps for diesel oxidation catalysts
US6375910B1 (en) * 1999-04-02 2002-04-23 Engelhard Corporation Multi-zoned catalytic trap and methods of making and using the same
JP3855266B2 (en) * 2001-11-01 2006-12-06 日産自動車株式会社 Exhaust gas purifying catalyst
US20040001781A1 (en) * 2002-06-27 2004-01-01 Engelhard Corporation Multi-zone catalytic converter
JP2005248787A (en) * 2004-03-03 2005-09-15 Mitsubishi Fuso Truck & Bus Corp Exhaust cleaner
DE102004040549B4 (en) * 2004-08-21 2017-03-23 Umicore Ag & Co. Kg Catalytically coated particle filter and its use
US7481983B2 (en) * 2004-08-23 2009-01-27 Basf Catalysts Llc Zone coated catalyst to simultaneously reduce NOx and unreacted ammonia
JP2006125206A (en) 2004-10-26 2006-05-18 Ict:Kk Purification method and device for internal combustion engine exhaust gas
GB2406803A (en) * 2004-11-23 2005-04-13 Johnson Matthey Plc Exhaust system comprising exotherm-generating catalyst
US7576031B2 (en) * 2006-06-09 2009-08-18 Basf Catalysts Llc Pt-Pd diesel oxidation catalyst with CO/HC light-off and HC storage function
RU2438777C2 (en) * 2006-08-19 2012-01-10 Умикоре Аг Унг Ко. Кг Filter of diesel engine exhaust gas solid particles, methods of its fabrication and application
US7534738B2 (en) * 2006-11-27 2009-05-19 Nanostellar, Inc. Engine exhaust catalysts containing palladium-gold
JP5103052B2 (en) * 2007-04-17 2012-12-19 東京濾器株式会社 Oxidation catalyst of exhaust gas purification system for diesel engine
WO2010077843A2 (en) * 2008-12-29 2010-07-08 Basf Catalysts Llc Oxidation catalyst with low co and hc light-off and systems and methods
US9440192B2 (en) * 2009-01-16 2016-09-13 Basf Corporation Diesel oxidation catalyst and use thereof in diesel and advanced combustion diesel engine systems

Also Published As

Publication number Publication date
US20100257843A1 (en) 2010-10-14
WO2010118125A3 (en) 2011-03-24
CN102387856A (en) 2012-03-21
US8637426B2 (en) 2014-01-28
BRPI1015175A2 (en) 2016-04-19
EP2416877A4 (en) 2013-04-17
JP2012523313A (en) 2012-10-04
KR20190073617A (en) 2019-06-26
KR20170045399A (en) 2017-04-26
KR20120014893A (en) 2012-02-20
WO2010118125A2 (en) 2010-10-14
BRPI1015175B1 (en) 2018-09-11
JP5730282B2 (en) 2015-06-10
EP2416877A2 (en) 2012-02-15

Similar Documents

Publication Publication Date Title
EP2461895B2 (en) Treatment system for gasoline engine exhaust gas
CN104147925B (en) Diesel particulate filter having a thin coating of catalytic oxidation
CN105642116B (en) For filtering out the filter of particulate matter from the tail gas that positive ignition engine is discharged
EP2763791B1 (en) Oxidation catalyst for internal combustion engine exhaust gas treatment
US7875573B2 (en) Pt-Pd diesel oxidation catalyst with CO/HC light-off and HC storage function
EP1992409B1 (en) Selective catalytic reduction type catalyst, and exhaust gas purification equipment and purifying process of exhaust gas using the same
JP5787768B2 (en) Laminated diesel oxidation catalyst composite material
CN101820997B (en) Catalyst compositions
EP2643078B1 (en) Three-way catalytic system having an upstream multi-layer catalyst
JP5095389B2 (en) Exhaust gas treatment catalyst
JP6023590B2 (en) Catalyst product and method and system for treating lean combustion diesel exhaust stream using the same
JP5447757B2 (en) Catalyst coated particle filter, process for its production and use thereof
JP5756026B2 (en) Diesel oxidation catalyst composite for high hydrocarbon conversion with layer structure
KR20110126622A (en) Diesel oxidation catalyst composite with layer structure for carbon monoxide and hydrocarbon conversion
US8475752B2 (en) NOx adsorber catalyst with superior low temperature performance
KR20130131343A (en) Three-way catalytic system having an upstream single-layer catalyst
EP2561195B1 (en) Gasoline engine emissions treatment systems having gasoline particulate filters
US8057768B2 (en) Device for the purification of diesel exhaust gases
CN102325580B (en) Exhaust gas treatment system and method having a catalytic scr scr filter and the downstream catalyst,
KR20140110932A (en) Catalysed substrate monolith
US20090022641A1 (en) Multilayered catalyst compositions
KR101621983B1 (en) Gasoline engine emissions treatment systems having particulate traps
KR20160003725A (en) Filter substrate comprising zone-coated catalyst washcoat
EP2501464B1 (en) Zoned catalyzed soot filter
EP2427637B1 (en) Improved lean hc conversion of twc for lean burn gasoline engines

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
C14 Grant of patent or utility model